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CAS No. : | 105-87-3 | MDL No. : | MFCD00015037 |
Formula : | C12H20O2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | - |
M.W : | 196.29 | Pubchem ID : | - |
Synonyms : |
NSC 2584;Geranyl ethanoate;Geraniol acetate
|
Num. heavy atoms : | 14 |
Num. arom. heavy atoms : | 0 |
Fraction Csp3 : | 0.58 |
Num. rotatable bonds : | 6 |
Num. H-bond acceptors : | 2.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 60.13 |
TPSA : | 26.3 Ų |
GI absorption : | High |
BBB permeant : | Yes |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -4.63 cm/s |
Log Po/w (iLOGP) : | 2.83 |
Log Po/w (XLOGP3) : | 4.04 |
Log Po/w (WLOGP) : | 3.24 |
Log Po/w (MLOGP) : | 2.95 |
Log Po/w (SILICOS-IT) : | 2.98 |
Consensus Log Po/w : | 3.21 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 1.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -3.21 |
Solubility : | 0.122 mg/ml ; 0.000622 mol/l |
Class : | Soluble |
Log S (Ali) : | -4.3 |
Solubility : | 0.00993 mg/ml ; 0.0000506 mol/l |
Class : | Moderately soluble |
Log S (SILICOS-IT) : | -2.52 |
Solubility : | 0.597 mg/ml ; 0.00304 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 2.0 |
Synthetic accessibility : | 2.72 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P264-P280-P302+P352+P332+P313+P362+P364-P305+P351+P338+P337+P313 | UN#: | N/A |
Hazard Statements: | H315-H319 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With pyridine Ambient temperature; | |
100% | With pyridine In tetrahydrofuran at 0 - 20℃; | |
99% | With pyridine; dmap at 20℃; for 1h; |
99% | With dmap In dichloromethane for 1h; | |
99% | at 20℃; for 6h; | |
99% | With [{CpHf(OH2)3}2(μ2-OH)2][OSO2C8F17]4*4H20*2THF at 20℃; for 0.0833333h; chemoselective reaction; | |
99% | With Cp2Ti(OSO2C8F17)2 at 20℃; for 0.0833333h; Neat (no solvent); | |
99% | With pyridine at 20℃; for 5h; Inert atmosphere; | |
98% | With pyridine Ambient temperature; | |
98% | With pyridine at 20℃; for 6h; | |
98% | With pyridine; dmap at 20℃; for 6h; | |
98% | With lanthanum(III) nitrate at 20℃; for 0.25h; | |
98% | With pyridine at 20℃; for 6h; | |
98% | With dmap; potassium carbonate In ethyl acetate at 20℃; for 1h; | |
97% | With dmap; triethylamine In dichloromethane at 0℃; for 0.333333h; Inert atmosphere; | |
97% | In dichloromethane at 20℃; for 1h; Inert atmosphere; | 1 A solution of geraniol (10.8 g, 70 mmol) in DCM (40 mL) under nitrogen was added acetic anhydride (13.2 mL, 140 mmol). Catalytic DMAP (428 mg, 3.5 mmol) was added and the mixture was stirred at room temperature for 1 hour. MeOH (20 mL) was added and the solution was stirred for another hour. Heptane (300 mL) was added and the mixture was washed with water (x2) and saturated NaHCC>3, dried (Na2S04), filtered and evaporated in vacuo to afford 13.3 g (97%) of the product. |
97% | In dichloromethane | 3.ci Synthesis was carried out with geraniol as a starting material. Geraniol was acetylated using pyridine and acetic anhydride in anhydrous dichloromethane to obtain an acetate (compound represented by (ci) below) (yield: 97%). |
96% | With dmap; triethylamine In dichloromethane at 20℃; for 8h; | |
96% | With H3[P(Mo3O10)4]*nH2O at 20℃; for 0.166667h; | |
96% | With 1,3-dichlorotetrabutyldistannoxane at 20℃; for 24h; | (iii) Acetylation of 2 with Ac2O in the presence of distannoxane 1 followed by columnchromatography using 10%-moist silica gel To an acetic anhydride solution (2.5 mL) of geraniol (2, 771 mg, 5.0 mmol) wasadded 1 (27.6 mg, 0.025 mmol as dimer, 0.02 mol% Sn) at rt, and the mixture wasstirred at rt for 24 h. After addition of NaHCO3 aqueous solution, an organic layer wasseparated, and the aqueous layer was extracted with AcOEt (3 times). The combinedorganic layer was washed with NH4Claq (twice) and then NaClaq, and dried overMgSO4. After evaporation, the crude product was subjected to columnchromatography on 10%-moist silica gel (AcOEt/hex 5:95) to afford geranyl acetate (3)in a pure form (938 mg, 4.8 mmol, 96%). |
95% | In pyridine at 20℃; for 12h; | |
95% | With La(NO3)3*6H2O | Synthesis of (E)-3,7-dimethyl-octa-2,6-dienyl acetate (7). To a mixture of alcohol/phenol/amine (1 mmol) and acetic anhydride(1.2 mmol), La(NO3)3·6H2O (10 mol%) was added. After completion of the reaction as monitored by using TLC, water was added to the reactionmixture, and the product was extracted into ethyl acetate(3×20 mL). The combined organic layers were washed with brine and concentrated in vacuum, which was purified by using silica gelcolumn chromatography to afford the acetylated product 7. |
95% | With pyridine at 0 - 20℃; for 5h; | |
95% | With pyridine In dichloromethane | 2 (8-methoxy-3,7-dimethyl-dodeca-(2E,6E)-dienyl diphosphate(combination of compound represented by formula (B)) The target compound was synthesized using geraniol as a starting material. Use of pyridine and acetic anhydride in geraniol in anhydrous dichloromethaneAcetylation to give acetate(Compound represented by the following formula (bi)) (yield 95%).Next, the 8-position carbon of the acetate is selenized in ethanol.An aldehyde body (a compound represented by the following formula (bii)) was obtained (yield 24%).Next, the aldehyde is subjected to alkaline hydrolysis with potassium hydroxide.An alcohol (compound represented by the following formula (biii)) was formed (yield 38%).Next, the alcohol is treated with imidazole, tert-butyldiphenylchlorosilane (TBDPS) in anhydrous dichloromethane.The compound shown in the following (biv) was obtained (yield 80%).Then, the compound is reacted with butyllithium in an anhydrous ether to obtain a butyl alcohol (the following formula (bv))Compound represented) (yield 73%).Next, the compound is converted to the sodium salt in anhydrous tetrahydrofuran, followed by the sodiumAdding methyl iodide to the salt and passing the Williamson synthesis,An ether (the compound represented by the following (bvi)) was obtained (yield 95%).Next, the ether is subjected to elimination reaction using tetra-n-ammonium fluoride in anhydrous tetrahydrofuran.An alcohol (a compound represented by the following formula (bvii)) was obtained (yield 87%).Next, N-chlorosuccinimide is used in an anhydrous dichloromethane solvent below -40 ° C.Chlorine substitution with dimethyl sulfide on the primary hydroxyl group to give chloride (described below)(bviii) Compound represented) (yield 92%). Next, the chloride is diphosphorylated with tris(tetra-n-butylammonium) hydrogenated diphosphoric acid in anhydrous acetonitrile to obtain the target product (the compound represented by the following formula (bix), which is represented by the formula (B). Compound) (yield 26%). |
94% | In pyridine | |
94% | With Nafion-H In dichloromethane at 20℃; for 3h; | |
94% | With dmap In dichloromethane at 0 - 20℃; for 24h; Schlenk technique; | |
93% | With triethylamine In dichloromethane at 20℃; | |
93% | With pyridine In dichloromethane at 20℃; for 24h; Cooling with ice; | (E)-3,7-Dimethyl-octa-2,6-dienyl acetate (geranyl acetate) ((E)-19 Acetic anhydride (0.72 mL, 7.70 mmol) was added dropwise to an ice-cooled solution of geraniol (1.08 g, 7.00 mmol), dry pyridine (1.47 mL) in dichloromethane (10 mL). After warming to room temperature, the mixture was stirred for 24 h. Water (20 mL) and dichloromethane (20 mL) were then added and the aqueous layer was extracted with dichloromethane (20 mL). The combined organic layers were washed successively with saturated NaHCO3 (10 mL) and brine (10 mL), dried and evaporated under reduced pressure to yield geranyl acetate (E)-19 as a colorless oil (1.28 g, 6.5 mmol, 93%). |
93% | With triethylamine In dichloromethane at 0 - 25℃; for 15.5h; Inert atmosphere; Cooling with ice; | |
91% | With TEA In dichloromethane at 20℃; | |
90% | With copper(II) bis(trifluoromethanesulfonate) at -25℃; for 7h; | |
90% | With perchloric acid at 20℃; for 1h; | |
90% | With pyridine Inert atmosphere; | |
90% | With dmap; triethylamine In dichloromethane at 0 - 20℃; for 24h; Inert atmosphere; | |
88% | With triethylamine In dichloromethane at 0 - 20℃; | |
87% | With dmap; triethylamine In dichloromethane | |
87% | With triethylamine In dichloromethane at 20℃; Inert atmosphere; | |
85% | With pyridine In diethyl ether | |
85% | With ruthenium(III) 2,4-pentanedionate at 25℃; for 8h; | |
84% | In pyridine for 4h; Ambient temperature; | |
84% | With o-benzenedisulfonimide at 20℃; for 0.0166667h; | |
84% | With pyridine; dmap at 20℃; for 2h; Inert atmosphere; | |
83% | With nickel dichloride for 0.133333h; microwave irradiation; | |
82% | With pyridine at 20℃; for 12h; | |
80% | With bismuth oxide perchlorate at 20℃; for 1h; | |
71% | With dmap In dichloromethane at 20℃; for 1h; Inert atmosphere; | 2 To a solution of geraniol (1b, 4.45 g, 28.8 mmol) in dichloromethane (15 ml) were added DMAP (175 mg, 1.43 mmol) and acetic anhydride (6.0 ml, 63 mmol) and the mixture was stirred at room temperature under nitrogen for 1 h. After addition of methanol (10 ml), the reaction mixture was further stirred for 1 h, diluted with diethyl ether, washed twice with aq. 4% sodium hydrogen carbonate, distilled water, and brine, and dried over sodium sulfate. The solvents were evaporated and the residue was purified with FCC (hexane:ethyl acetate = 20:1) to give geranyl acetate (2b, 4.04 g, 20.6 mmol) in 71% yield: colorless oil; 1H NMR (CDCl3, 400 MHz) δ = 5.34 (1H, t, J = 7 Hz, 2-H), 5.08 (1H, t, J = 7 Hz, 6-H), 4.58 (2H, d, J = 7 Hz, CH2O), 2.13-2.03 (4H, m, 3-CH2CH2), 2.06 (3H, s, 1-OCOCH3), 1.70 (3H, s, 3-CH3), 1.68 (3H, s, 7-CH3 trans to C6-CH2), 1.60 (3H, s, 7-CH3 cis to C6-CH2); |
50.8% | With 5% MoO3 modified mesoporous silica In cyclohexane at 35℃; for 0.5h; | |
With Lipase PS In hexane at 30℃; for 24h; var. substrates and reagent concentrations; var. incubation time and temp.; other solvents; also in the presence of water; | ||
at 110℃; | ||
With diethyl ether; benzylmagnesium chloride Zersetzen des Reaktionsproduktes mit Eis; | ||
With sodium acetate | ||
With camphor-10-sulfonic acid | ||
With sodium acetate at 140 - 150℃; | ||
With pyridine | ||
With pyridine; dmap for 2h; 0 deg C --> rt; | ||
In pyridine | ||
In pyridine at 15℃; for 15h; | ||
58.5 g | In pyridine for 1.5h; | |
With pyridine In dichloromethane for 4h; Ambient temperature; | ||
With pyridine; dmap In dichloromethane Ambient temperature; | ||
With pyridine; dmap | ||
With pyridine In dichloromethane | ||
With pyridine at 20℃; | ||
95 % Chromat. | In acetonitrile at 25℃; for 8.5h; | |
84 % Chromat. | With lithium perchlorate at 25℃; for 9h; | |
With dmap; triethylamine In dichloromethane at 20℃; | ||
With phosphoric acid | ||
96 % Chromat. | With Bu3O In dichloromethane at 25℃; for 14h; | |
With dmap; triethylamine In dichloromethane at 20℃; for 2h; | ||
98.8 % Chromat. | In water at 200℃; for 0.00275h; | |
With pyridine at 20℃; for 15h; | ||
With pyridine; dmap at 20℃; Inert atmosphere; | ||
With triethylamine In dichloromethane at 20℃; for 16h; | ||
With dmap In dichloromethane at 20℃; Schlenk technique; | ||
With cesium 12-tungstophosphate at 20℃; for 0.5h; Green chemistry; | ||
With C12H8N2*2CH4O3S at 50℃; for 2h; | 2.4. Esterification of geraniol Geraniol (1.54 g, 0.01 mol) and acetic anhydride (1.02 g,0.01 mol) were added to a 100 mL three neck round bottom flask and heated to a designed temperature. Then 1a (0.074 g,0.2 mmol) was added to the mixture and stirred at 50 °C for 2 h. 1a was separated from the reaction system by easy decantation. The yield of geranyl acetate was determined by GC-MS with an internal standard (n-butyl acetate). The proposed mechanism for the reaction of geraniol with acetic anhydride with the use of PGTACs as catalyst is shown in Scheme 2. | |
With immobilized enzyme Novozym 435<SUP>®</SUP> at 130℃; for 0.166667h; Enzymatic reaction; | ||
90 %Spectr. | With sulfonated biochar at 20.1℃; for 4h; | |
With dmap; triethylamine In dichloromethane at 20℃; for 1h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99.9% | With Candida antarctica lipase B at 50℃; for 4h; Molecular sieve; Ionic liquid; Green chemistry; Enzymatic reaction; | |
99.2% | With hydroquinone at 120℃; | 1-13 Add 60.05g of acetic acid, 178.58g of geraniol and 1.92g of hydroquinone into a 500mL three-necked flask, place it in a water bath and heat it, add 3.84g of catalyst 732 cation exchange resin when the thermometer value reaches 120, and turn it on Stirring: After turning on the stirring, take a sample every 30 minutes, and perform acid value titration and chromatographic analysis on it. Stop the experiment when the acetic acid content is basically stable. |
97% | With 1,3-propanesultone; N-ethyl-N-methylbutan-1-amine; toluene-4-sulfonic acid at 110℃; for 2h; | 3 Examples 1 to 5 Take 14.48g of acetic acid and 30.84g geraniol,Evenly mixed into the three bottles,Plus 5g acidic functionalized ionic liquid catalyst I,Heated to reflux mixing,Use diverter to divert water,110 reaction 2h,After cooling with ether extraction,Raffinate for the recovery of the catalyst,Decompression recovery of ether,Distilled geranyl acetate,Yield in Table 1;_Among them, the acidic functionalized ionic liquid catalyst I prepared as follows:Propane 1,3-propane sultonewithMethyl ethyl butylamine at a molar ratio of 1: 1,The reaction at 40 10h to give a white solid,The white solid was washed with ethyl acetate to dry.One equivalent of the above white solid was slowly added to a reaction vessel containing 1 molar equivalent of p-toluenesulfonic acid under an ice-water bath,The reaction was stirred for 2h,Then heated to 80 reaction 8h,After washing with ethyl acetate,The ethyl acetate was distilled off under reduced pressure to obtain an ionic liquid catalyst I,The catalyst is a colorless viscous liquid. |
93% | Stage #1: acetic acid With iodine; triphenylphosphine In dichloromethane at 20℃; for 0.166667h; Stage #2: With gadolinium(III) trifluoromethanesulfonate In dichloromethane at 50℃; for 0.5h; Stage #3: Geraniol In dichloromethane | |
89% | With cobalt(II) chloride at 60℃; for 10h; | |
85% | With 2,3-dicyano-5,6-dichloro-p-benzoquinone for 1h; Heating; | |
100 % Chromat. | With Candida antarctica lipase SP382 In hexane at 30℃; for 24h; Candida antarctica lipase SP382; other Candida antarctica lipases; var. temperature and reaction time, other solvents, var. concentrations of substrates; effect of water contents; | |
With hydrogenchloride; tetrachloromethane | ||
With hydrogenchloride; benzene | ||
With hydrogenchloride; diethyl ether | ||
With dmap In dichloromethane at 20℃; for 20h; | ||
With N,N′,N′′,N′′′-hexadecyltrimethylammonium bis(trifluoromethylsulfonyl)imide; Novozym 435 (immobilized Candida antarctica lipase B) at 50℃; for 4h; Green chemistry; Enzymatic reaction; | Lipase-catalyzed synthesis of flavour esters in sponge-like ionic liquid (SLILs) Three mmol of citronellol, geraniol, nerol or anisyl alcohol, and 1, 2 or 3mmol of acetic acid were added to 3mL screw-capped vials with teflon-lined septa. Then, the corresponding amount of [C16tma][NTf2] was added to reach a final IL concentration of 60 or 70% (w/w) with respect to the mass substrates. Reaction mixtures were pre-incubated at 50°C for 10min, resulting in fully clear monophasic systems. Then, 80mg of MS13× per mmol of carboxylic acid were also added. The reaction was started by adding Novozym 435 (40mg/mmol of carboxylic acid) and the reaction was incubated for 4h at 50°C while shaking (300rpm), or under 4W microwave irradiation (which provided a 50°C constant temperature). For products analysis, aliquots (20μL) were taken at selected times and suspended in 500μL octane, and the resulting biphasic mixture was shaken to extract the products. The resulting mixture was centrifuged at 14,000rpm for 10min. Finally, 300μL of the octane extract were added to 100μL of a 100mM ethyl propionate (internal standard) solution in octane, and the final solution was analyzed by CG. For full recovery of the flavour ester products at 4h, the reaction mixtures were consecutively centrifuged four times at 14,000rpm (15min) and at room temperature, 21, 10 and 4°C, which resulted in a top liquid phase of flavour ester and a bottom solid phase containing the SLIL. For the case of anisyl acetate, the reaction mixture was cooled in an ice bath for 3h, and the resulting solid mixture was placed in a centrifugal filter, then centrifuged at 16,000rpm (10min) and at 0°C. This resulted in a top SLIL solid phase, which was retained inside the filter, and a bottom liquid phase of anisyl acetate. For all cases, a sample (10μL) of the resulting flavour ester phase was dissolved in 1mL acetone-δ6, then analyzed by 300MHz 1H NMR and 282MHz 19F NMR, in a Brucker AC 300E spectrometer for SLIL detection. All experiments were carried out in duplicate. | |
at 59.84℃; for 3h; | ||
With sulfuric acid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
41% | With selenium(IV) oxide; In ethanol; for 22h;Reflux; | Geranyl acetate (7) (6.84 g, 34.9 mmol) pre-dissolved in 100 mL of 95% ethanol was added dropwise over 40 min to a refluxing solution of SeO2(5.8 g, 52 mmol) in 300 mL of 95% ethanol. The mixture was heated under reflux for 22 h. The black precipitate was removed by vacuum filtration over a pad of silica-gel, and washed with 95% ethanol. Solvent was removed at reduced pressure, and 400 mL of ethyl ether was added. Organic layer was washed with brine (4×80 mL), dried overNa2SO4, and concentrated under vacuum. The residue was purified byusing silica gel column chromatography to give a light yellow oil(2.8 g) with a yield of 41%. |
24% | In ethanol; | Next, the carbon atom at position 8 was subjected to selenium oxidation in ethanol to obtain an aldehyde form (compound represented by (bii) below) (yield: 24%). |
Example 8General Preparation of Lycophyll 2HCrocetindialdehyde (238) was obtained from SynChem, Inc. (Des Plaines, Ill.) as a brick-red solid and was used without further purification. Lycopene was obtained from ChromaDex (Santa Ana, Calif.) as a red solid and was used without further purification. Acetic acid 3,7-dimethyl-8-oxo-octa-2,6-dienyl ester (230a) (Liu and Prestwich 2002) was synthesized by literature procedures from commercially available geranyl acetate (228a). All other reagents and solvents used were purchased from Across Organics (Morris Plains, N.J.) and Sigma-Aldrich (St. Louis, Mo.) and were used without further purification. All reactions were performed under a nitrogen atmosphere. All flash chromatographic purifications were performed on Natland International Corporation 230-400 mesh silica gel using indicated solvents. LC/MS (APCI and ESI+modes) were recorded on an Agilent 1100 LC/MSD VL system; column: Zorbax Eclipse XDB-C18 Rapid Resolution (4.6×75 mm, 3.5 μm); temperature: 25'.C; flow rate: 1.0 mL/min.; mobile phase (A=0.025% TFA in H2O, B=0.025% TFA in acetonitrile). Gradient program (for intermediates 230a-236a and 216a): 70% A/30% B (start), step gradient to 50% B over 5 minutes, step gradient to 100% B over 1.3 minutes, hold at 100% B over 4.9 minutes. Gradient program (for intermediates 218a, 2H): 70% A/30% B (start), step gradient to 50% B over 5 minutes, step gradient to 98% B over 3.3 minutes, hold at 98% B over 16.9 minutes. All-trans lycophyll was obtained from crude material using a Waters 996 Photo Diode Array detector, Millipore 600E System Controller and Waters 717 Autosampler; column: YMC C30 Carotenoid S-5, (10×250 mm, 5 μm column); temperature: 25 C.; flow rate: 4.7 mL/min; mobile phase (A=methanol (MeOH), B=methyl-t-butyl ether (MTBE)) Gradient program: 60% A/40% B (start), step gradient to 80% A over 1 minute, hold at 80% A over 119 minutes. Fractions were collected from 55-66 minutes. Fraction analysis was performed on a YMC C30 Carotenoid S-5, (4.6×250 mm, 5 μm column). Proton nuclear magnetic resonance (NMR) spectra were obtained on a Varian Unity INOVA 500 spectrometer operating at 500.111 MHz (megahertz). Electronic absorption spectra were recorded on a Cary 50 Bio UV-Visible spectrophotometer. |
With tert.-butylhydroperoxide; selenium(IV) oxide; In dichloromethane; water; for 48h; | Procedure adapted from literature procedures.15 Selenium dioxide (0.742 g, 6.68 mmol, 14mol %) was suspended in 75 ml DCM in a 500 ml round bottom flask. tert-Butyl hydroperoxide (25 ml,186.8 mmol, 2 equiv.; Luperox 70 wt. % in H2O) was added and the reaction was stirred for 30 min generating a clear, biphasic solution. Geranial acetate (20 ml, 93.3 mmol; Alfa Aesar) was added via syringe. A reflux condenser was attached and the reaction was stirred for 48 h without heating. The reaction was diluted with 100 ml MeOH and cooled to 0 C. Sodium borohydride was added slowly until aldehyde not observed by TLC (Rf = 0.52 (2:1 Hex:EtOAc; KMnO4). Solution turned from clear to red toyellow to clear during this process. The reaction was diluted with another 100 ml DCM and 100 ml H2O | |
With tert.-butylhydroperoxide; selenium(IV) oxide; silica gel; salicylic acid; In dichloromethane; at 20℃; for 26h;Inert atmosphere; | A suspension of selenium dioxide (5.6 mg, 1.0 mmol) tert-butyl hydroperoxide (0.24 mL, 2.5 mmol), salicylic acid (12 mol%, 16.6 mg) in anhydrous dichloromethane (20 mL) was stirred for 20 min at room temperature, and then silica gel (230-400 mesh, 72.0 mg) was added. After 30 min, the geranyl acetate 9 (196.3 mg,1.0 mmol) was slowly added. The mixture was stirred for 26 h, filtered through Celite, and washed with 10% potassium hydroxide and brine. The extract was dried over Na2SO4 and concentrated under vacuum. The resulting dark orange residue was dissolved in 4 mL of ethanol and cooled to 0 C, and sodium borohydride (37.8 mg, 1.0 mmol) was added in several portions. After 30 min, a saturated solution of NH4Cl (5 mL), brine, and ethyl acetate was added. The mixture was extracted with ethyl acetate and once with dichloromethane, dried, and concentrated. The residue was purified by flash chromatography eluting with hexane/AcOEt (9/1, v/v) to give alcohol 10 as a yellow oil (160.0 mg, 75%). 1H NMR (400 MHz, CDCl3): δ (ppm)5.38-5.28 (m, 2H), 4.55 (2H, d, J 7.2), 3.96 (2H, s), 2.28-2.06 (5H,m), 2.05 (3H, s), 1.70 (3H, s), 1.60 (3H, s). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With pyridine; ozone In dichloromethane at -78℃; Inert atmosphere; Stage #2: With dimethylsulfide In dichloromethane at -78 - 23℃; Inert atmosphere; | |
71% | Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With 3-chloro-benzenecarboperoxoic acid In dichloromethane at -10 - 20℃; Stage #2: With periodic acid In tetrahydrofuran; diethyl ether at 0℃; for 0.5h; | |
66% | Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With pyridine; ozone In dichloromethane at -78℃; Stage #2: With triphenylphosphine In dichloromethane at -78 - 20℃; for 4h; |
66% | With ozone In dichloromethane at -78℃; for 6.5h; | |
57% | 50 Example 50 Example 50 : 6-Acetoxy-4-methylhex-4E-enal The title compound was prepared in 57% yield from geranyl acetate (see Example 49), using the ozonolysis-zinc-acetic acid reduction procedure, taught by E. J. Corey, K. Achiwa, J. A. Katzenellenbogen, J. Amer. Chem. Soc. , 91, 4318 (1969). Analytical Data : NMR (CDCl3)δ: 1.8 (3 H, bs), 2.1 (3 H, s), 2.4-2.8 (4 H, m), 4.6 (2 H, bd, J=2 Hz) 5.4 (1 H, bt, J=7 Hz), 9.9 (1 H, bt). | |
55% | Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; for 0.5h; Inert atmosphere; Stage #2: With hydrogenchloride; sodium periodate In tetrahydrofuran; water at 20℃; for 1.5h; Inert atmosphere; | |
50% | Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With ozone In dichloromethane at -78℃; Stage #2: With dimethylsulfide In dichloromethane for 12h; Further stages.; | |
(i) KMnO4, tBuOH, (ii) aq. HIO4; Multistep reaction; | ||
(i) O3, CH2Cl2, Py, (ii) Zn, AcOH; Multistep reaction; | ||
With pyridine; ozone In dichloromethane | ||
With ozone | ||
With ozone-containing oxygen; zinc 1.) methylene dichloride, piridine, -78 grad C, 2.) AcOH, 2 h, room temp.; Multistep reaction; | ||
oxidation; | ||
With ozone; acetic acid; zinc 1.) methylene chloride, -78 degC, 4.5 h; 2.) room t., 2 h; Yield given. Multistep reaction; | ||
With dimethylsulfide; ozone Yield given. Multistep reaction; | ||
With pyridine; dimethylsulfide; ozone 1.) CH2Cl2, -78 deg C; Yield given. Multistep reaction; | ||
Multi-step reaction with 2 steps 1: MCPBA / CH2Cl2 / 2 h / 0 - 20 °C 2: H5IO6 / tetrahydrofuran; H2O / 3 h / 0 - 20 °C | ||
Multi-step reaction with 2 steps 1: 92.8 percent / m-chloroperoxybenzoic acid / CH2Cl2 / 0 - 5 °C 2: 73.6 percent / periodic acid / diethyl ether; tetrahydrofuran / 1.5 h / 20 °C | ||
Multi-step reaction with 2 steps 1: 100 percent / mCPBA / CH2Cl2 / 2 h / -20 - 20 °C 2: HIO4*2H2O / diethyl ether; tetrahydrofuran / 0.5 h / 0 °C | ||
Multi-step reaction with 2 steps 1: 47 percent / K2CO3; K3Fe(CN)6; K2OsO4 / 2-methyl-propan-2-ol; H2O / 72 h / 4 °C 2: 98 percent / aq. NaIO4 / acetone / 0 - 20 °C | ||
Multi-step reaction with 2 steps 1.1: NBS; water / tetrahydrofuran / 0.5 h / 20 °C 1.2: aq. KOH / tetrahydrofuran / 1 h / 20 °C 2.1: 11.1 g / aq. HClO4; KIO4 / tetrahydrofuran / 0.5 h / 20 °C | ||
Multi-step reaction with 2 steps 1: 81 percent / MCPBA / CH2Cl2 / 4 h / 20 °C 2: 71 percent / aq. HIO4 / tetrahydrofuran / 0.5 h / 0 °C | ||
Multi-step reaction with 2 steps 1: 76 percent / mCPBA / diethyl ether / 6 h / 0 °C 2: 85 percent / NaIO4 / dioxane; H2O / 24 h / Ambient temperature | ||
Multi-step reaction with 2 steps 1: 84 percent / mCPBA / CH2Cl2 / 12 h / Ambient temperature 2: 97 percent / H5IO6 / tetrahydrofuran; H2O / 1.5 h / Ambient temperature | ||
Multi-step reaction with 2 steps 1: 98 percent / n-CPBA, NaOAc / CH2Cl2 / 2 h / 0 °C 2: HIO4*2H2O / diethyl ether; tetrahydrofuran / 0.5 h / 0 °C | ||
Multi-step reaction with 2 steps 1: N-Methyl-morpholine N-oxide monohydrate, osmium tetraoxide / acetone; tetrahydrofuran; H2O / 1). 18 h, room temperature, 2) 12 h, 50 deg C 2: Sodium periodate / dioxane; H2O / 1.5 h / 0 - 5 °C | ||
Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With 3-chloro-benzenecarboperoxoic acid In dichloromethane Stage #2: With periodic acid In tetrahydrofuran; water Further stages.; | ||
Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With sodium acetate; 3-chloro-benzenecarboperoxoic acid In dichloromethane at -21℃; Stage #2: With periodic acid In tetrahydrofuran; diethyl ether at 0℃; Further stages.; | ||
Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With ozone In dichloromethane at -78℃; Stage #2: With dimethylsulfide In dichloromethane at -78 - 20℃; | ||
With ozone; triphenylphosphine In dichloromethane | 27; 27.a Aldehyde 95 known in the document (J. Am. Chem. Soc. 2005, 127, 7014-7024) which was prepared from a commercially available product 29 in accordance with the method (a) was converted to Compound 30 of which the chain is extended in accordance with the method (b) (Org. Lett. 2007, 9, 1461-1464) (55% yield for 2 steps). | |
Multi-step reaction with 2 steps 1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 4 h / 0 °C / Inert atmosphere 2: sodium periodate; H(1+)*IO4(1-)*2H2O=HIO4*2H2O / tetrahydrofuran; water / 1 h / 0 °C / Inert atmosphere | ||
Multi-step reaction with 2 steps 1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 4 h / -5 - 0 °C 2: periodic acid dihydrate / diethyl ether; tetrahydrofuran / 5 h / 0 °C | ||
Multi-step reaction with 2 steps 1: 3-chloro-benzenecarboperoxoic acid / dichloromethane 2: periodic acid / tetrahydrofuran | ||
Multi-step reaction with 2 steps 1: 3-chloro-benzenecarboperoxoic acid / dichloromethane 2: periodic acid / water; tetrahydrofuran | ||
With ozone; triphenylphosphine In dichloromethane | 27 Aldehyde 95 known from literature (J. Am. Chem. Soc. 2005, 127, 7014-7024), which can be obtained from commercially available 29 by procedure (a), was converted into 30 whose carbon chain was extended by procedure (b) (Org. Lett. 2007, 9, 1461-1464) (55% yield for 2 steps). | |
Multi-step reaction with 2 steps 1: 3-chloro-benzenecarboperoxoic acid / diethyl ether / -30 - 0 °C 2: sodium periodate / 1,4-dioxane; water / 24 h / 20 °C | ||
Multi-step reaction with 2 steps 1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 1 h / 0 °C 2: sodium periodate / acetonitrile; water / 12 h / 20 °C | ||
Multi-step reaction with 2 steps 1: 3-chloro-benzenecarboperoxoic acid / diethyl ether / 12 h / -30 - 0 °C 2: sodium periodate; water / 1,4-dioxane / 24 h / 20 °C | ||
Multi-step reaction with 2 steps 1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 0 - 20 °C 2: sodium periodate; periodic acid / tetrahydrofuran; water / 1.17 h / 0 - 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With N-Bromosuccinimide In 1,4-dioxane; water at 0 - 20℃; for 5h; | |
70% | With [bis(acetoxy)iodo]benzene; water; lithium bromide In acetonitrile at -10℃; for 0.25h; Inert atmosphere; regioselective reaction; | General procedure C: bromohydroxylation General procedure: To a solution of the geranyl derivative (1.0 equiv) in acetonitrile(0.1 M) cooled to -10 °C, DIB (1.4 equiv) was added. A solution of lithium bromide (1.6 equiv) in H2O (0.1 M) wasthen added dropwise over 5 min. After stirring at -10 °C for10 min, the reaction mixture was diluted with EtOAc, filteredover alumina (EtOAc) and concentrated under reduced pressurebefore purification by flash chromatography. |
With N-Bromosuccinimide In water; <i>tert</i>-butyl alcohol |
With N-Bromosuccinimide; water In 1,2-dimethoxyethane at 0℃; for 2h; | ||
With N-Bromosuccinimide; water In tetrahydrofuran for 0.75h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With diphenyl diselenide; magnesium sulfate at 66 - 68℃; electrolysis under a constant current 6.7 mA/cm2; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 30% 2: 76 % Spectr. 3: 30 % Spectr. 4: 36% | In chloroform at 25℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 36% 2: 76 % Spectr. 3: 30 % Spectr. 4: 30% | With benzophenone tosylhydrazone In chloroform at 25℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With ortho-N,N-dimethylamino benzylthiolatocopper(I) In tetrahydrofuran; toluene at -30℃; for 0.0833333h; | |
With [CuSC6H4(CH2NMe2)-2]3 In tetrahydrofuran at -30℃; for 0.0833333h; | ||
In tetrahydrofuran at -30℃; for 0.0833333h; Yield given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With lithium chloride In N,N-dimethyl-formamide at 10℃; for 38h; other condition: CH2CHSnBu3, 23 deg C, 20 h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With lithium chloride In N,N-dimethyl-formamide at 23℃; for 47h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With lithium chloride In N,N-dimethyl-formamide at 23℃; for 22h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With lithium chloride In N,N-dimethyl-formamide at 60℃; for 48h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With triphenylphosphine In tetrahydrofuran for 36h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With triphenylphosphine In tetrahydrofuran for 5h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at -20 - 20℃; for 2h; | |
99% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; for 1h; | |
98% | With sodium acetate In dichloromethane at 0℃; for 2h; |
96% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; for 4h; | |
96% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; for 4h; Inert atmosphere; | |
92% | With oxaziridinium salt [C10H12NO(1+)*BF4(1-)] In dichloromethane for 0.5h; | |
92.8% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0 - 5℃; | |
92% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane | 11.kii The olefin at position 6 was oxidized using m-chloroperbenzoic acid in anhydrous dichloromethane to obtain an epoxy form (compound represented by (kii) below) (yield: 92%). |
92% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; for 1h; | (E)-5-(3,3-Dimethyl-oxiranyl)-3-methylpent-2-enyl acetate 27 To a cold (0°C) soln. of geranyl acetate 26 (10 g, 50.9 mmol) in DCM (100 ml) was slowly added a soln. of mCPBA (13.82 g, 56.04 mmol, ca. 70%) in DCM (60 ml) over 15 min. The resulting mixture was stirred for 45 min. until the complete conversion of substrate (TLC control). The aq. NaOH soln. (3M, 30 ml) was added and phases were separated. The water layer was extracted with DCM (3 x 35 ml), combined organic extracts were washed with brine (2 x 30 ml) and dried over anhydrous Na2SO4. Filtration and evaporation in vacuo furnished crude product as a yellow oil (10.5 g) that was purified by FLC (90 g SiO2, hexanes/Et2O, gradient elution 6:1 → 3:1) yielding pure epoxide 27 as a colourless oil (9.95 g, 92%). |
91% | With sodium hydrogencarbonate; 3-chloro-benzenecarboperoxoic acid In dichloromethane; water at 0℃; | |
88% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane; chloroform for 12h; | |
87.4% | With sodium hydrogencarbonate; 3-chloro-benzenecarboperoxoic acid In dichloromethane for 2h; Ambient temperature; | |
86% | With sodium hydrogencarbonate; 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; for 1.75h; | |
85% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0 - 20℃; for 3h; | |
85% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; for 3h; | |
84% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane for 12h; Ambient temperature; | |
83% | With dirhodium(II) tetrakis(triphenylacetate); bis(tertbutylcarbonyloxy)iodobenzene; water In 2,2,2-trifluoroethanol at 20℃; for 16h; | |
81% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; for 4h; | |
81% | With Rf2Bimpy; oxygen; isobutyraldehyde In chlorobenzene; acetone at 40℃; for 1h; | |
81% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane | |
78% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0 - 20℃; | |
77% | With maleic anhydride; urea-hydrogen peroxide complex In dichloromethane for 6h; Ambient temperature; | |
76% | With 3-chloro-benzenecarboperoxoic acid In diethyl ether at 0℃; for 6h; | |
75% | With phosphotungstic acid; sulfuric acid; urea hydrogen peroxide adduct In water; isopropyl alcohol at 20℃; for 0.25h; Inert atmosphere; | |
74% | With rhodium(II) acetate dimer; oxygen; isobutyraldehyde In acetone at 20℃; | 4.2 General procedure General procedure: A two-neck round bottom flask was charged with Rh2(OAc)4 (4.4 mg, 0.01 mmol), and alkene (1.0 mmol) followed by addition of acetone (3.0 mL). A dry-ice condenser was attached to the flask, then, isobutyraldehyde (274 μL, 3.0 mmol) was added; and a constant flow of oxygen was introduced to the system via an oxygen-filled balloon. Reaction completion was monitored by GC-MS. When the reaction was complete, solvent was removed under reduced pressure and the oily residue was separated by flash chromatography using ether-hexanes solvent mixtures. All epoxide product spectroscopic data were in accord with literature data. |
73% | With 3-chloro-benzenecarboperoxoic acid In chloroform for 0.5h; | |
72% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at -5 - 0℃; for 4h; | (E)-5-(3,3-Dimethyloxiran-2-yl)-3-methylpent-2-enyl Acetate (4) A solution of m-chloroperbenzoic acid (85%, 18.1 g) in CH2Cl2 (160 mL) was added to a solution of 3 (15.0 g, 76.5 mmol) in CH2Cl2 (235 mL) at -5 °C over 2 h. The resulting mixture was stirred at 0 °C for 2 h. The white precipitate was formed during the reaction (mainly m-chlorobenzoic acid). The reaction mixture was diluted withsaturated aqueous NaHCO3 (250 mL) and the aqueous layer was extracted with CH2Cl2 (2 × 30 mL).The combined organic layer was washed with saturated aqueous NaHCO3, brine and dried (anhydrous MgSO4), and concentrated under reduced pressure. The residue was chromatographed on silica gel using 10% EtOAc/petroleum ether, affording 11.8 g (72%) of 4 as a colorless oil. 1H-NMR (300 MHz,CDCl3): δ = 5.42-5.37 (m, 1H, =CH-), 4.59 (d, 2H, J = 7.2 Hz,-CH2O-), 2.70 (t, 1H, J = 6.3 Hz,oxirane-H ), 2.26-2.13 (m, 2H, -CH2-), 2.05 (s, 3H, -CH3CO-), 1.73 (s, 3H, -CH3), 1.70-1.63 (m, 2H,-CH2-), 1.31 (s, 3H, -CH3), 1.26 (s, 3H, -CH3). ESI-MS (m/z): 235.2 (M+Na)+. |
71% | With N-hydroxyphthalimide; 1,1-Diphenylmethanol; oxygen; Hexafluoroacetone In benzonitrile at 80℃; for 20h; | |
71% | With sodium dihydrogenphosphate; phosphoric acid; dihydrogen peroxide; methyl tri-n-octyl ammonium hydrogen sulfate In toluene at 70℃; for 2h; | |
71% | With sodium hydrogencarbonate; 3-chloro-benzenecarboperoxoic acid In dichloromethane at 20℃; | |
69% | With dihydrogen peroxide; ethenetetracarbonitrile In acetonitrile for 12h; Ambient temperature; | |
67% | With oxygen; isobutyraldehyde In acetonitrile Ambient temperature; | |
67% | With oxygen; isobutyraldehyde In acetonitrile at 25℃; for 24h; | |
63% | With CoCl2*bis((4,5-dihydro-4-isopropyl)-oxazol-2-yl)methane; oxygen; isobutyraldehyde In acetonitrile Ambient temperature; | |
63% | With 2,4-bisperfluorooctylphenyl butyl selenide; water; dihydrogen peroxide In benzene at 70℃; | |
60% | With CoCl2*ephedrine; oxygen; isobutyraldehyde In 1,2-dichloro-ethane Ambient temperature; Co(II)*bis(4,5-dihydro-4-isopropyl)-oxazolyl-2)methane complex, var. solvent; | |
57.1% | With 3-chloro-benzenecarboperoxoic acid In diethyl ether at -30 - 0℃; | 8A.1 Synthesis of (E)-5-(3,3-dimethyloxiran-2-yl)-3-methylpent-2-en-l-yl acetate In a 250 mL round bottom flask, a solution of geranyl acetate (2.0 g, 10.20 mmol) in diethyl ether (20 mL) was treated with a solution of mCPBA (5.01 g, 30.60 mmol) in diethyl ether (20 mL) dropwise at -30°C. Once the addition was complete, the temperature was allowed to rise to 0°C. The reaction mixture was stirred at same temperature for 6 h and then placed overnight in a cold room (+3°C). After completion of the reaction (TLC), the reaction mixture was washed with 1 N NaOH (pH >10) and later with water till the washings were neutral pH. The extract was washed with brine, dried over anhydrous Na2S04 and solvent was removed under reduced pressure. The crude residue was purified by silica gel column chromatography (elution, 10% EtOAc in hexanes) to afford the title compound. Yield: 1.21 g (57.1%). (0453) 1H NMR (300 MHz, CDC : δ 5.38 (t, J = 6.0 Hz, 1H), 4.60 (d, J = 1.2 Hz, 2H),2.72 (t, J = 6.3 Hz, 1H), 2.23-2.12 (m, 2H), 2.04 (s, 3H), 1.72 (s, 3H), 1.69-1.62 (m, 2H), 1.30 (s, 3H), 1.26 (s, 3H) |
57.1% | With 3-chloro-benzenecarboperoxoic acid In diethyl ether at -30 - 0℃; for 12h; | |
47% | With oxygen; 2-ethoxycarbonyl-1-cyclopentanone In acetonitrile at 60 - 70℃; | |
With potassium carbonate; 3-chloro-benzenecarboperoxoic acid or NBS; Multistep reaction; | ||
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; for 0.166667h; Yield given; | ||
87 % Turnov. | With <Fe3O(piv)3(MeOH)3>Cl; oxygen at 60℃; for 20h; | |
With lutidine N-oxide In benzene Ambient temperature; | ||
With pyridine; N-Bromosuccinimide; acetic anhydride 1.) THF, water, 0 deg C, 1.5 h, 2.) THF, water, RT, 18 h; Yield given. Multistep reaction; | ||
With pyridine; N-Bromosuccinimide; acetic anhydride; potassium carbonate Yield given. Multistep reaction; | ||
With 3-chloro-benzenecarboperoxoic acid In dichloromethane for 0.5h; | ||
With sodium hydrogencarbonate; 3-chloro-benzenecarboperoxoic acid In dichloromethane for 48h; | ||
With Oxone; 2,2,2-Trifluoroacetophenone; sodium carbonate In acetonitrile at 0℃; for 2h; | ||
With 3-chloro-benzenecarboperoxoic acid | ||
Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With N-Bromosuccinimide; water In tetrahydrofuran at 20℃; for 0.5h; Stage #2: With potassium hydroxide In tetrahydrofuran at 20℃; for 1h; Further stages.; | ||
With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0 - 20℃; for 2h; | ||
Multi-step reaction with 2 steps 1: N-bromosuccinimide; H2O / tetrahydrofuran / 0.75 h 2: K2CO3; methanol / 0.33 h | ||
7.1 g | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0 - 20℃; for 1h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 19% 2: 68% | With Ni(dmp)2; oxygen; isobutyraldehyde In 1,2-dichloro-ethane for 13h; Ambient temperature; | |
1: 19.1% 2: 67.9% | With oxygen; isobutyraldehyde In 1,2-dichloro-ethane for 13h; Ambient temperature; | |
53% | With pyridine; dihydrogen peroxide In dichloromethane; water at -0.15℃; for 24h; Yield given; |
1: 11 % Chromat. 2: 86 % Chromat. | With cetylpyridinium peroxotungstophosphate; dihydrogen peroxide In chloroform; water Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With pyridine; dihydrogen peroxide In tetrahydrofuran; water at 19.85℃; for 2.4h; Yields of byproduct given; | |
1: 1 % Spectr. 2: 3 % Spectr. 3: 79 % Spectr. | With 2,6-lutidine N-oxide; trans-dioxo(5,10,15,20-tetramesitylporphirinato)ruthenium(VI) In benzene for 48h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 38% 2: 50% | With oxygen; isobutyraldehyde In 1,2-dichloro-ethane for 7h; Ambient temperature; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With formic acid; triethylamine In tetrahydrofuran for 3h; Heating; | |
100 % Chromat. | With ammonium formate In 1,4-dioxane for 2h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With tert.-butylhydroperoxide; selenium(IV) oxide; salicylic acid In dichloromethane at 20℃; for 20h; | |
74% | Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With selenium(IV) oxide In ethanol at 90℃; for 1h; Inert atmosphere; Stage #2: With sodium tetrahydroborate In methanol at 25℃; for 2h; Inert atmosphere; | |
74% | Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With tert.-butylhydroperoxide; selenium(IV) oxide; salicylic acid In dichloromethane; water at 0℃; for 22h; Stage #2: With sodium tetrahydroborate at 0℃; | (2E,6E)-8-Hydroxy-3,7-dimethylocta-2,6-dien-1-yl Acetate (8). In a 250 mL roundbottom flask, SeO2 (188 mg, 1.7 mmol), salicylic acid (550 mg, 4 mmol), and t-BuOOH(20 mL of 70% solution in H2O) were added sequentially to CH2Cl2 (60 mL) and themixture was stirred for 30 min at 0 °C, then geranyl acetate (7, 8.6 mL, 40 mmol) wasadded. The biphasic mixture was stirred for an additional 22 h at 0 °C and thenconcentrated under reduced pressure at below 30 °C. After Et2O (30 mL) was added, theorganic layer was washed with 10% KOH (10 mL, 4 times), H2O (8 mL, 3 times), and brine(10 mL), dried (Na2SO4), and finally concentrated in vacuo. The initial product waspurified by gradient column chromatography (hexane:EtOAc = 7:3) to afford compound 8(5.8 g, 63%) as a colorless oil. A second fraction contained the corresponding aldehyde,which was reduced to the alcohol by slow addition of °NaBH4 at 0 C to give an additional 1.01 g of the compound 8. Material from both fractions was combined to give a total yieldof 74%, with spectral data in accord with the literature.1 |
73% | With tert.-butylhydroperoxide; selenium(IV) oxide In dichloromethane Ambient temperature; | |
73% | With tert.-butylhydroperoxide; salicylic acid In dichloromethane at 25℃; for 25h; | |
73% | With tert.-butylhydroperoxide; selenium(IV) oxide In dichloromethane at 20℃; for 15h; | |
73% | Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With tert.-butylhydroperoxide; selenious acid In dichloromethane; water at 20℃; for 0.25h; Stage #2: With salicylic acid In dichloromethane at 20℃; | Preparation of (2E,6E)-8-((tert-butyldiphenylsilyl)oxy)-3,7-dimethylocta-2,6-dien-1-ol; coupling partner c Step (i): H2SeO3 (0.059 g, 0.459 mmol, 0.03 equiv) and tBuOOH (70% in water, 5.47 mL, 38.2mmol, 2.5 equiv) were added to a solution of geranyl acetate (3.28 mL, 15.28 mmol, 1 equiv) inCH2Cl2 (30 mL) at room temperature. After 15 minutes, salicylic acid neat (0.211 g, 1.528 mmol,0.1 equiv) was added to the reaction mixture and stirred overnight. Reaction was monitored byTLC (EtOAc/Heptane: 1/1, Rf= 0.59). After completion, the reaction mixture was concentratedunder reduced pressure and extracted in diethyl ether (100 mL). The organic phase was washedsuccessively with 3 M NaOH (3x50 mL), water (3x50 mL) and solution of NaCl sat. (30 mL),dried over Na2S04 and concentrated under reduced pressure. The resulting residue was purifiedby flash chromatography (loaded onto 100 g of silica and eluted with a gradient ofheptane/EtOAc starting at 100-0% and going to 0-100%) to afford the desired (2E,6E)-8-hydroxy-3,7-dimethylocta-2,6-dien-1-yl acetate as a colorless oil (m=1.217 g, colorless oil, 73%). |
68% | Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With tert.-butylhydroperoxide; selenium(IV) oxide In dichloromethane; water at 20℃; for 36h; Stage #2: With sodium tetrahydroborate In methanol; dichloromethane; water at 0℃; | |
60% | Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With tert.-butylhydroperoxide; selenium(IV) oxide; silica gel In dichloromethane for 24h; Stage #2: With sodium tetrahydroborate In ethanol at 0℃; Further stages.; | |
59% | Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With tert.-butylhydroperoxide; selenium(IV) oxide; salicylic acid In dichloromethane; water at 0 - 20℃; for 24h; Stage #2: With methanol; sodium tetrahydroborate at -10℃; for 0.75h; | 1 8-Hydroxy-geranyl acetate (G2) The solution of iert-butyl hydroperoxide in water (70%, 9.40 mL) was added to the suspension of Se02(210 mg, 1.89 mmol) and salicylic acid (261 mg, 1.89 mmol) in CH2Cl2(50 mL) and stirring was continued at RT. After 30 min. the mixture was cooled down to 0°C and the solution of geranyl acetate (5.0 g, 25.4 mmol) in CH2Cl2(5 mL) was added dropwise. The resulting mixture was stirred at 0°C for 5 min., then at RT for 24 h. The solvent was removed under vacuum, the residue was dissolved in Et20 (50 mL). The organic phase was washed with the saturated Na2S203aq. solution, water and brine, dried over anhydrous Na2S04, filtered and evaporated to dryness under vacuum. The oily residue was dissolved in methanol (40 mL), the solution was cooled to -lO°C and at this temperature NaBH4(0.l5 g, 40 mmol) was added portionwise during 15 min. After 30 min., the cold saturated NH4Cl aq. (50 mL) solution was added and the product was extracted with CH2Cl2(3x50 mL). The combined organic extracts were washed with water and brine, dried over anhydrous Na2S04, filtered and evaporated to dryness. The residue was purified by distillation (p=0.04 mbar, 70°C) to give (2E,6E)-8-hydroxy- 3,7-dimethylocta-2,6-dien-l-yl acetate G2 (oil, 3.2 g, 15.02 mmol, 59%). A sample for the NMR study was purified by column chromatography.500 MHz) d 5.38-5.33 (m, 2H, -Gtf=CH2-), 4.59 (d, 2H, -0-CZ-CH=), 3.99 (s, 2H, C2-OH), 2.20-2.15 (m, 2H, -CH2-C-CH=), 2.11-2.08 (m, 2H, -CH2-CU2- CH=), 2.06 (s, 3H, CHs-C OOR), 1.71 (s, 3H, -CH3), 1.67-1.62 (m, 4H);13C NMR (CDCl3, 125 MHz) d 171.2, 141.7, 135.2, 125.2, 118.6, 68.8, 61.4, 39.0, 25.6, 21.0, 16.35, 13.63. |
56% | Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With tert.-butylhydroperoxide; selenium(IV) oxide In dichloromethane at 25℃; for 8h; Stage #2: With sodium tetrahydroborate In ethanol at 0℃; for 1h; | |
55% | With selenium(IV) oxide | |
55% | Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With selenium(IV) oxide In ethanol at 24℃; Reflux; Inert atmosphere; Stage #2: With sodium tetrahydroborate In diethyl ether; ethanol at 0℃; for 4h; Inert atmosphere; | |
49% | With tert.-butylhydroperoxide; selenium(IV) oxide; salicylic acid In dichloromethane at 20℃; for 24h; | |
49% | With tert.-butylhydroperoxide; selenium(IV) oxide; salicylic acid In dichloromethane; water at 20℃; for 24h; | |
49% | With tert.-butylhydroperoxide; selenium(IV) oxide; benzoic acid In dichloromethane | |
48% | With tert.-butylhydroperoxide; selenium(IV) oxide In dichloromethane at 20℃; | |
47% | Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With tert.-butylhydroperoxide; selenium(IV) oxide; salicylic acid In dichloromethane; water for 42h; Stage #2: With methanol; sodium tetrahydroborate at 0℃; for 1h; | |
46% | With tert.-butylhydroperoxide; selenium oxide; salicylic acid In dichloromethane; water at 0 - 20℃; for 48h; | 2 The above acetate 2b (1.02 g, 5.20 mmol) was dissolved in dichloromethane (10 ml) and cooled down to 0 °C, to which were added an aqueous 70% tert-butyl hydroperoxide solution (1.8 ml, 13 mmol), salicylic acid (88 mg, 0.64 mmol), and selenium oxide (30 mg, 0.27 mmol). The mixture was stirred at room temperature for 2 days and the reaction was quenched with distilled water. After extraction with diethyl ether, the organic phase was washed twice with distilled water and brine and dried over sodium sulfate. All the solvents were evaporated and the residue was purified with FCC (hexane:ethyl acetate = 4:1) to give 8-hydroxy-farnesyl acetate (3b, 505 mg, 2.38 mmol) in 46% isolated yield: colorless oil; 1H NMR (CDCl3, 600 MHz) δ = 5.38-5.33 (2H, m, 2-, 6-H), 4.58 (2H, d, J = 7 Hz, CH2OAc), 3.99 (3H, s, 7-CH2), 2.19-2.08 (4H, m, 3-CH2CH2), 2.05 (3H, s, 1-OCOCH3), 1.71 (3H, s, 7-CH3), 1.66 (3H, s, 3-CH3) [The 8-OH was invisible.]; |
43% | With tert.-butylhydroperoxide; selenium(IV) oxide; salicylic acid In dichloromethane at 20℃; Inert atmosphere; | |
40% | With tert.-butylhydroperoxide; selenium(IV) oxide In dichloromethane Ambient temperature; | |
38% | With tert.-butylhydroperoxide; selenium(IV) oxide | 8.hii Next, the compound was subjected to oxidation reaction with selenium dioxide and tert-butyl hydroperoxide to obtain a trans alcohol form (compound represented by (hii) below) (yield: 38%). |
With selenium(IV) oxide | ||
With tert.-butylhydroperoxide; selenium(IV) oxide | ||
With tert.-butylhydroperoxide; sodium tetrahydroborate; selenium(IV) oxide 1.) CH2Cl2, 4 deg C, 20 h; 2.) EtOH, 0 deg C; Yield given. Multistep reaction; | ||
With sodium tetrahydroborate; selenium(IV) oxide 1.) 95percent ethanol, reflux, 1 h; Yield given. Multistep reaction; | ||
With tert.-butylhydroperoxide; sodium tetrahydroborate; selenium(IV) oxide 1.) CH2Cl2, 2.) EtOH; Yield given. Multistep reaction; | ||
With sodium tetrahydroborate; selenium(IV) oxide 1.) 96percent ethanol, reflux, 10 h; 2.) ether/methanol (3:1), ice cooling; Yield given. Multistep reaction; | ||
With tert.-butylhydroperoxide; sodium tetrahydroborate; selenium(IV) oxide 1.) CH2Cl2, RT, 3 h, 2.) methanol, 0 deg C, 10 min; Yield given. Multistep reaction; | ||
With tert.-butylhydroperoxide; sodium tetrahydroborate; selenium(IV) oxide 1.) dichloromethane, rt., 3 h; 2.) methanol, 0 deg C, 10 min; Yield given. Multistep reaction; | ||
With tert.-butylhydroperoxide; selenium(IV) oxide; dimethylsulfide; benzoic acid 1.) CH2Cl2, RT, 26 h, 2.) reflux, 6 h; Yield given. Multistep reaction; | ||
With tert.-butylhydroperoxide; sodium tetrahydroborate; selenium(IV) oxide 1.) CH2Cl2, RT, 3 h, 2.) methanol, RT, 0.5 h; Yield given. Multistep reaction; | ||
With tert.-butylhydroperoxide; selenium(IV) oxide; salicylic acid In dichloromethane | ||
With tert.-butylhydroperoxide; sodium tetrahydroborate; selenium(IV) oxide; 4-hydroxy-benzoic acid 1.) CH2Cl2, room temperature, 18 h, 2.) MeOH, 0 deg C, 1 h; Yield given; Multistep reaction; | ||
With tert.-butylhydroperoxide; selenium(IV) oxide; salicylic acid In dichloromethane | ||
Multi-step reaction with 2 steps 1: 9 percent / SeO2; t-BuO2H; 4-hydroxybenzoic acid / CH2Cl2 2: NaBH4 / ethanol / 1 h / 0 °C | ||
Multi-step reaction with 2 steps 1: SeO2 / H2O; dioxane 2: NaBH4 / ethanol / 1 h / 20 °C | ||
Multi-step reaction with 2 steps 1: 40 percent / SeO2, t-BuOOH / toluene / 120 h / Ambient temperature 2: NaBH4 / ethanol / 0 - 20 °C | ||
Multi-step reaction with 2 steps 1: 61 percent / ZnCl2 / various solvent(s) / 1.5 h / -20 °C 2: 93 percent / P(OMe)3 / methanol / 1.5 h / 50 - 60 °C | ||
Multi-step reaction with 2 steps 1: SeO2 / aq. ethanol / 1 h / Heating 2: NaBH4 / diethyl ether; methanol / 0.75 h | ||
Multi-step reaction with 2 steps 1: 44 percent / SeO2 / aq. ethanol / 9 h / Heating 2: 72 percent / NaBH4 / methanol / 5 h / -10 °C | ||
Multi-step reaction with 2 steps 1: 44 percent / SeO2 / aq. ethanol / 9 h / Heating 2: NaBH4 / aq. ethanol / 0 °C | ||
Multi-step reaction with 4 steps 1: 2.) silica gel / 1.) CH2Cl2, -20 deg C, 10 min; 2.) hexane, ether 2: 73 percent / p-TsOH*H2O / benzene / 6 h / 45 °C / in the dark 3: NaIO4 / methanol; H2O / 20 h / 20 °C 4: (MeO)3P / methanol / 48 h / 20 °C | ||
Multi-step reaction with 2 steps 1: 40 percent / SeO2 / aq. ethanol / 1 h / Heating 2: 91 percent / NaBH4 | ||
Multi-step reaction with 2 steps 1: SeO2 / ethanol / 3 h / Heating 2: 2 percent / NaBH4 / diethyl ether; ethanol / 30 h / 0 °C | ||
Multi-step reaction with 3 steps 1: (i) CH2Cl2, (ii) H2O, hexane 2: TsOH / benzene 3: (i) NaIO4, (ii) P(OMe)3, MeOH | ||
Multi-step reaction with 2 steps 1: SeO2 2: NaBH4 | ||
Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With tert.-butylhydroperoxide; selenium(IV) oxide; salicylic acid In dichloromethane at 0℃; Stage #2: With sodium tetrahydroborate In ethanol at 0℃; Stage #3: With water; ammonium chloride In ethanol | ||
Multi-step reaction with 2 steps 1: selenium(IV) oxide / ethanol / 1 h / Reflux 2: ethanol; sodium tetrahydroborate / 1 h / 0 °C | ||
40 mg | With selenium(IV) oxide; ethanol for 2h; Inert atmosphere; Reflux; | |
Multi-step reaction with 2 steps 1: selenium(IV) oxide; 3-Chloro-2-hydroxybenzoic acid; tert.-butylhydroperoxide / dichloromethane; water / 24 h / 20 °C 2: sodium tetrahydroborate / ethanol / 0 - 20 °C | ||
Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With tert.-butylhydroperoxide; selenium(IV) oxide; salicylic acid In dichloromethane at 20℃; for 24h; Stage #2: With methanol; sodium tetrahydroborate at 20℃; for 2h; | 1 Selenium dioxide 0.221 g (0.002 mole) 90% t-butyl hydroperoxide 40 ml (0.36 mol), 1.4 g of salicylic acid (0.01 mol), dichloromethane 35 ml, 19.75 g, geranyl acetate (0.10 Mol) was added to a round bottom flask and the reaction was stirred at room temperature for 24 hours. The reaction mixture was then washed with sodium bisulfite and saturated brine. Then, it was extracted three times with dichloromethane, dried over anhydrous sodium sulfate, filtered and the filtrate was concentrated under reduced pressure at 30 °C. The obtained oil was added with 20 ml of methanol and 3.8 g of sodium borohydride, and the mixture was stirred at room temperature for 2 hours. The reaction mixture was quenched with 1 mol / l dilute sulfuric acid and extracted three times with ethyl acetate. The organic phase was dried over anhydrous sodium sulfate and the filtrate was removed by filtration. The filtrate was concentrated under reduced pressure and the resulting oil was distilled under vacuum (2E,6E)-8-hydroxy-3,7-dimethyl-2,6-diene decanol acetate (yield 59%). | |
Multi-step reaction with 2 steps 1: selenium(IV) oxide / 1,4-dioxane; ethanol / 5 h / 80 °C / Inert atmosphere 2: sodium tetrahydroborate / methanol / 1 h / -10 °C / Inert atmosphere | ||
12.78 g | With sodium tetrahydroborate In methanol; dichloromethane; water at 0℃; | (2E,6E)-8-hydroxy-3,7-dimethylocta-2,6-dien-1-yl acetate (S22). Procedure adapted from literature procedures.15 Selenium dioxide (0.742 g, 6.68 mmol, 14mol %) was suspended in 75 ml DCM in a 500 ml round bottom flask. tert-Butyl hydroperoxide (25 ml,186.8 mmol, 2 equiv.; Luperox 70 wt. % in H2O) was added and the reaction was stirred for 30 min generating a clear, biphasic solution. Geranial acetate (20 ml, 93.3 mmol; Alfa Aesar) was added via syringe. A reflux condenser was attached and the reaction was stirred for 48 h without heating. The reaction was diluted with 100 ml MeOH and cooled to 0 °C. Sodium borohydride was added slowly until aldehyde not observed by TLC (Rf = 0.52 (2:1 Hex:EtOAc; KMnO4). Solution turned from clear to red toyellow to clear during this process. The reaction was diluted with another 100 ml DCM and 100 ml H2O and transferred to a separatory funnel rinsing with DCM and H2O. The layers were separated and theaqueous layer was extracted with DCM 2x. The organic layer was washed with sat. NaCl, dried with MgSO4, filtered, and concentrated. The crude reaction was purified via flash column chromatography to yield 12.78 g (59%) of (2E,6E)-8-hydroxy-3,7-dimethylocta-2,6-dien-1-yl acetate as a pale yellow oil. Spectral data matches literature.16 1H NMR (300 MHz, CDCl3) δ 5.39-5.32 (m, 2H), 4.58 (d, J = 7.1 Hz,2H), 3.99 (s, 2H), 2.21-2.14 (m, 2H), 2.11-2.03 (m, 2H), 2.05 (s, 3H), 1.70 (s, 3H), 1.66 (s, 3H) 1.46 (s,1H). Rf = 0.32 (2:1 Hex:EtOAc; KMnO4). |
Multi-step reaction with 2 steps 1: silica gel; salicylic acid; selenium(IV) oxide; tert.-butylhydroperoxide / dichloromethane / 26 h / 20 °C / Inert atmosphere 2: sodium tetrahydroborate / dichloromethane / 0.5 h / 0 °C / Inert atmosphere | ||
With tert.-butylhydroperoxide; selenium(IV) oxide In dichloromethane at 20℃; for 1.5h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
45%; 19% | With selenium(IV) oxide; tert-butyl hydroperoxide; In dichloromethane; at 0℃; for 5h;Inert atmosphere; | General procedure: Starting material (1.00 mmol) was added to a solution of selenium dioxide (44 mg, 0.40 mmol) and t-BuOOH (453 mg, 3.10 mmol) in dichloromethane (5 mL) at 0C. After stirring under nitrogen at 0C for a time t (vide infra), the mixture was diluted with ethyl acetate (15 mL), and washed successively with water (2 x 10 mL), saturated NaHCO3 (10 mL), water (10 mL) and brine (10 mL). The organic layer was then dried over MgSO4 and evaporated under reduced pressure. The crude product was purified by chromatography on silica gel (hexanes / ethyl acetate). |
With selenium(IV) oxide; In ethanol; for 1h;Reflux; | SeO2 (4.34 g, 37.9 mmol) was added to a solution of geranyl acetate (Compound 29, 7.7 ml, 36 mmol) in EtOH (20 ml) at room temperature, and the mixture was refluxed for one hour. The reaction solution was allowed to warm to room temperature, and was filtered through celite. The filtrate was concentrated, and the residue was then subjected to column chromatography on silica gel (Hexane:EtOAc = 1:1). The fractions containing alcohol (Compound 30) and aldehyde (Compound 31) were collected. After evaporation of the solvent, the residue was dissolved in Et2O (100 ml). MnO2 (85% purity, 22.5 g, 220 mmol) was added to this solution followed by stirring for 15 hours. The reaction solution was filtered through celite, and the filtrate was washed with a saturated aqueous NaCl solution, and was dried over Na2SO4. After evaporation of the solvent, the residue was purified by column chromatography on silica gel (Hexane:EtOAc = 4:1) to yield the aldehyde (Compound 31) (2.142 g, 28%). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
69% | With diphenyl diselenide; water; magnesium sulfate In acetonitrile at 66 - 68℃; electrolysis under a constant current 6.7 mA/cm2; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
70% | With AD-mix-α; methanesulfonamide In water; <i>tert</i>-butyl alcohol at 0℃; for 48h; | |
66% | With potassium osmate(VI); methanesulfonamide; potassium hexacyanoferrate(III) In water; <i>tert</i>-butyl alcohol at 20℃; for 48h; | (S,E)-6,7-dihydroxy-3,7-dimethyloct-2-enyl acetate (4)[1]: General procedure: To a solution of geranyl acetate 3 (6.2 g, 31.6 mmol) in 380 mL of 1:1 t-BuOH-H2O was added (DHQ)2PHAL (0.24 g, 0.32 mmol), K2OsO4 (0.025 g, 0.06 mmol), K3Fe(CN)6 (31 g, 94.9 mmol), K2CO3 (13.1 g, 94.5 mmol), CH3SO2NH2 (3 g, 31.6 mmol), at room temperature. After stirring for 48 h, the resulting yellow suspension was treated with sodium sulfite (40 g) and stirred for 25 min. After removal of t-BuOH under reduced pressure ,the mixture was extracted with DCM (3 x 100 mL), the combined organic layers were washed with water, and then brine(100 mL), dried over anhydrous Na2SO4, filtered and concentrated to give the crude product which was further purified by silica gel chromatography (PE/EA = 2:1) to give (S,E)-6,7-dihydroxy-3,7-dimethyloct-2-enyl acetate (4) (5 g, 69%) as a colorless oil. |
47% | With potassium osmate(VI); potassium carbonate; potassium hexacyanoferrate(III) In water; <i>tert</i>-butyl alcohol at 4℃; for 72h; |
With osmium(VIII) oxide; sodium hydrogensulfite; 4-methylmorpholine N-oxide In water; acetone; <i>tert</i>-butyl alcohol at 50℃; for 12h; | ||
With osmium(VIII) oxide; 4-methylmorpholine N-oxide In tetrahydrofuran; water; acetone 1). 18 h, room temperature, 2) 12 h, 50 deg C; Yield given; | ||
With osmium(VIII) oxide; methanesulfonamide; potassium carbonate; potassium hexacyanoferrate(III) In water; <i>tert</i>-butyl alcohol Ambient temperature; | ||
Multi-step reaction with 2 steps 1: 73 percent / m-CPBA / CHCl3 / 0.5 h 2: 78 percent / 60percent HClO4 / 1,2-dimethoxy-ethane / 2 h / 30 °C | ||
Multi-step reaction with 2 steps 1: 1) mCPBA, 2) K2CO3 / or NBS 2: acid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With chloro-trimethyl-silane; dimethyl sulfoxide In dichloromethane at 0℃; Sealed tube; regioselective reaction; | |
90% | With pyridine; sulfuryl dichloride In dichloromethane at -60 - 0℃; for 0.166667h; | |
86% | With trichloroisocyanuric acid at -10 - 0℃; for 6h; | 1 REFERENTIAL EXAMPLE 1 40 g (20.4 mmol) of geranil acetate was dissolved in 100 ml of n-hexane. After adding 17.1 g (70.0 mmol) of trichloroisocyanuric acid slowly, the mixture was maintained at -100 C. to 00 C. for six hours. After the completion of the reaction, remaining trichloroisocyanuric acid and by-produced isocyanuric acid were removed out of the system by filtration. The filtrate was washed with a 5% aqueous solution of sodium hydrogencarbonate and ion-exchange water in order, and dried over anhydrous sodium sulfate. After removal of the solvent, a crude product was obtained. The crude product was subjected to silica gel column chromatography to give desired 6-chloro-3,7-dimethyl-2,7-octatrienyl acetate as pale yellow oil in a yield of 86%. |
85% | With hypochlorous anhydride In tetrachloromethane; diethyl ether for 0.25h; Ambient temperature; | |
85% | With tetrabutyl-ammonium chloride; bis-[(trifluoroacetoxy)iodo]benzene In dichloromethane at 0℃; for 0.333333h; Inert atmosphere; chemoselective reaction; | General procedure E: allylic chlorination General procedure: To a solution of the geranyl derivative (1.0 equiv) in dichloromethane(stabilized with amylene, 0.1 M) cooled to 0 °C, PIFA(1.2 equiv) was added. A solution of tetra-n-butylammonium chloride (1.5 equiv) in DCM (0.1 M) was then added dropwiseover 10 min and the reaction mixture was stirred for 10 min at0 °C. The reaction mixture was diluted with EtOAc, Na2S2O3solution (10%) was added and the layers were separated. Theaqueous layer was extracted three times with EtOAc. Thecombined organic extracts were washed with water and brine,dried over MgSO4, filtered and concentrated under reducedpressure before purification by flash chromatography. |
83% | With tert-butylhypochlorite; silica gel | |
82% | With tert-butylhypochlorite; silica gel In hexane 1.) 0 deg C, 30 min, 2.) room temp., 1 h; | |
81% | With sodium chloride In dichloromethane; water for 4h; Ambient temperature; electrolysis by using Pt foils at constant current (50 mA); | |
81% | With chloro-trimethyl-silane; racemic methyl phenyl sulfoxide; dihydrogen peroxide In dichloromethane at 25℃; Flow reactor; regioselective reaction; | |
80% | With sulfuryl dichloride; sodium carbonate In dichloromethane at 0℃; | |
70% | With tert-butylhypochlorite; silica gel In hexane 1.) 0 deg C, 30 min, 2.) room temperature, 1 h; | |
63% | With sodium chloride In dichloromethane; water at 25℃; electrolysis: ruthenium oxide: anode; titanium cylinder: cathode; I = 0.94 A; | |
63% | With pyridine; sulfuryl dichloride In dichloromethane at 0℃; for 0.166667h; | |
39% | With sulfuryl dichloride In cyclohexane at 0 - 5℃; | |
With hypochloric acid In dichloromethane Yield given; | ||
With pyridine; sulfuryl dichloride In tetrachloromethane at -5 - 0℃; for 1h; | ||
With sodium carbonate; sodium thiosulfate In dichloromethane | 1 EXAMPLE 1 EXAMPLE 1 The synthesis of 6-chloro-3,7-dimethyl-2,7-octadienyl acetate. STR5 3,7-dimethyl-2,6-octadienyl acetate 20.00 g (102 mmol), dichloromethane 100 ml, and sodium hypochlorite aqueous solution (12.58%) 62.20 g (sodium hypochlorite 105 mmol) were placed in a flask. To the mixture, hydrochloric acid aqueous solution (1.18N) 95.0 ml (112 mol) was added in dropwise over a period of 45 minutes below 10° C. The mixture was stirred for further 15 minutes at 4° C. To the mixture, 100 ml of 10% sodium thiosulfate aqueous solution and 100 ml of 10% sodium carbonate aqueous solution were added successively and stirred for five minutes, and then the organic layer was separated. The aqueous layer was extracted with 100 ml of dichloromethane, and the extract was added to the organic layer. The organic solvent was distilled off under reduced pressure to give 26.32 g of colorless liquid. The crude product was found 78.6% purity of 6-chloro-3,7-dimethyl-2,7-octadienyl acetate by gas chromatography using n-tridecane as the internal standard. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With methanesulfonamide; AD-mix-β In <i>tert</i>-butyl alcohol at 0℃; for 24h; enantioselective reaction; | 4.4.1. (R,E)-6,7-Dihydroxy-3,7-dimethyloct-2-en-1-yl acetate ((R)-7) AD-mix-b (14 g, 10 mmol) and methanesulfonamide (951 mg,10 mmol) were added to a 1:1 mixture of t-BuOH:H2O (100 mL) andvigorously stirred for 15 min at room temperature. After cooling to0C, geranyl acetate (2.13 mL, 10 mmol) was added, the mixturewas stirred at that temperature for 24 h, then quenched with solidsodium metabisulte (13.5 g). The mixture was extracted severaltimes with dichloromethane and the combined organic layers werewashed with a 10% aq. NaOH solution and brine. The crude productwas puried by column chromatography on silica gel (hexane:ethylacetate 7:3) to afford the diol (R)-7 in 96% yield (2.20 g) as acolorless oil. [a]D25 26.1 (c 0.7, CHCl3), lit.28[a]D23 26.8(c 1.0, CHCl3). Following the same procedure with AD-mix-a, theenantiomeric diol (S)-7 was isolated in 90% yield (2.07 g).[a]D25 23.9 (c 0.9, CHCl3), lit.29[a]D20 25.1 (c 0.7, EtOH).1HNMR (500 MHz, CDCl3) d (ppm): 1.17 (s, 3H); 1.22 (s, 3H); 1.45 (m,1H); 1.62 (m, 1H); 1.73 (s, 3H); 1.91 (br s, 2H); 2.06 (s, 3H); 2.12 (m,1H); 2.32 (m, 1H); 3.45 (dd, J 10.5, 2.0 Hz, 1H) 4.59 (d, J 7.0 Hz,2H); 5.40 (br t, J 7.0 Hz, 1H).13C NMR (100 MHz, CDCl3) d (ppm):16.4; 21.01; 23.2; 26.5; 29.4; 35.6; 61.3; 73.0; 78.0; 118.7; 142.0;171.1. MS (EI): m/z 170 (M- AcOH, 1); 152 (3); 111 (18); 94 (32); 81(27); 68 (72); 59 (100); 43 (73). |
85% | With potassium osmate(VI) dihydrate; methanesulfonamide; potassium carbonate; (9S,9"S)-9,9"-[phthalazine-1,4-diylbis-(oxy)]bis[10,11-dihydro-6'-methoxycinchonane]; potassium hexacyanoferrate(III) In water; <i>tert</i>-butyl alcohol at 4℃; for 24h; Inert atmosphere; | |
80% | With AD-mi-β; water; <i>tert</i>-butyl alcohol at 0℃; for 15h; |
80% | With potassium osmate(VI); methanesulfonamide; potassium hexacyanoferrate(III); potassium carbonate; (9S,9"S)-9,9"-[phthalazine-1,4-diylbis-(oxy)]bis[10,11-dihydro-6'-methoxycinchonane] In water; <i>tert</i>-butyl alcohol at 4℃; for 12h; optical yield given as %ee; enantioselective reaction; | |
75% | With potassium osmate(VI); methanesulfonamide; DHQD-PYDZ; potassium carbonate; potassium hexacyanoferrate(III) In water; <i>tert</i>-butyl alcohol at 4℃; for 12h; | |
70% | With potassium osmate(VI); DHQD-PYDZ; potassium hexacyanoferrate(III) In water; <i>tert</i>-butyl alcohol at 4℃; for 12h; | |
46% | With methanesulfonamide; potassium carbonate; potassium hexacyanoferrate(III) In water; <i>tert</i>-butyl alcohol at 4℃; for 144h; | |
Multi-step reaction with 5 steps 1: 1.) SeO2; 2.) NaBH4 / 1.) 96percent ethanol, reflux, 10 h; 2.) ether/methanol (3:1), ice cooling 2: 68 percent / tetraisopropoxy orthotitanate, (-)-tartaric acid dimethylester, t-butylhydroperoxide 3: 90 percent / pyridine / 24 h / 0 °C 4: 1.) NaI; 2.) NaBH3CN / 1.) acetone, reflux, 4.5 h; 2.) THF/HMPT (4:1), 60 deg C, 3 h 5: 85 percent / H2O, conc. H2SO4 / tetrahydrofuran / 30 h / 0 °C | ||
Multi-step reaction with 5 steps 1: SeO2 / ethanol / 3 h / Heating 2: 2 percent / NaBH4 / diethyl ether; ethanol / 30 h / 0 °C 3: 79 percent / D-(-)-diisopropyl tartrate (D-(-)-DIPT), Ti(Oi-Pr)4, tert.-butyl hydroperoxide (TBHP) / CH2Cl2 / 4 h / -20 °C 5: 85 percent / 18 M H2SO4 / tetrahydrofuran; H2O / 30 h / 0 °C | ||
Multi-step reaction with 4 steps 1: 1) mCPBA, 2) K2CO3 / or NBS 2: acid 3: Swern's method 4: 96.5 percent / baker's yeast, glucose / H2O; ethanol / 72 h / Ambient temperature |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With N-iodo-succinimide; tetra-n-butylammonium dihydrogen trifluoride In dichloromethane at 0℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 62% 2: 9% 3: 5% | With ruthenium(IV) oxide; sodium periodate In water; ethyl acetate; acetonitrile at 0℃; for 0.0666667h; | |
1: 50% 2: 18% 3: 19% | With sodium periodate; ruthenium tetroxide In water; ethyl acetate; acetone at 25℃; for 0.0333333h; | |
1: 12% 2: 39% 3: 12% | With sodium periodate In tetrachloromethane; water; acetonitrile at 0℃; for 0.25h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With 3-(trimethylsilyl)-2-oxazolidinone; hydrogen bromide In dichloromethane at 0℃; for 0.5h; | |
95% | With 2,4,4,6-Tetrabromo-2,5-cyclohexadien-1-one; cetyltrimethylammonim bromide In dichloromethane; chloroform | |
91% | With [bis(acetoxy)iodo]benzene; lithium bromide In acetonitrile at 0℃; for 0.0833333h; Inert atmosphere; Molecular sieve; chemoselective reaction; |
91% | With [bis(acetoxy)iodo]benzene; lithium bromide In acetonitrile at 0℃; for 0.0833333h; Inert atmosphere; Molecular sieve; regioselective reaction; | General procedure A: dibromination General procedure: To a solution of the geranyl derivative (1.0 equiv) in acetonitrile(0.05 M) at 0 °C, lithium bromide (2.0-2.4 equiv),4 Å molecular sieves (1.0 mass equiv) and DIB (1.2-1.4 equiv) were added. After stirring for 5 min, the reaction mixture wasdiluted with EtOAc, filtered over alumina (EtOAc) and concentratedunder reduced pressure before purification by flash chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
68% | With 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; for 1h; Inert atmosphere; | |
With aluminum oxide; 4 A molecular sieve; iodine; pyridine hydrochloride 1.) dry CH2Cl2, 30 min, room temp, 2.) CH2Cl2, 20 h; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With N,N'-biscyclohexyl-imidazol-2-ylidene; 5A molecular sieve In tetrahydrofuran at 20℃; for 0.5h; | |
97% | With caesium carbonate at 125℃; for 25h; | |
94% | With heterogeneous zinc/imidazole catalyst at 90℃; for 5h; Inert atmosphere; Schlenk technique; |
90% | With aluminum oxide; monoaluminum phosphate at 25℃; | |
90% | With recombinant acyltransferase from Mycobacterium smegmatis In aq. phosphate buffer at 25℃; for 24h; Green chemistry; Enzymatic reaction; | |
With Mucor miehei lipase at 55 - 60℃; for 8h; | ||
With Novozyme-435 at 20℃; for 48h; Sealed tube; Enzymatic reaction; | Typical Procedure for Acetylation General procedure: The experiments were performed with 100 mg of substrate, 5 mg of Novozyme-435 and 5 mL of ethyl acetate (Tables 2 and 3). The suspension containing a mixture of the lipase and the corresponding substrate in ethyl acetate was stirred with a magnetic stirring bar in a test tube sealed with a cap at room temperature, being monitored by TLC. After reaction completion, the stirring was stopped and the solution filtered through a cotton plug. The solvents were evaporated under vacuum and the residue analyzed by 1H and 13C NMR spectra (provided in the supplemental information) to confirm the structure and determine the percentage of conversion of the primary alcohols into their corresponding acetylated forms | |
With immobilized enzyme Novozym 435<SUP>®</SUP> at 50℃; for 1h; Enzymatic reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With potassium fluoride on basic alumina In toluene for 2h; | |
94% | With dmap; triethylamine at 0℃; for 3h; | |
84% | With pyridine at 0 - 20℃; for 5h; | (E)-3,7-Dimethylocta-2,6-dienyl Acetate (3) To a stirred solution of geraniol (2, 30.0 g, 194.8 mmol)in pyridine (80 mL) was added dropwise CH3COCl (16.5 mL) at 0 °C over 2 h, and the resulting mixture was stirred at room temperature for 3 h. The reaction mixture was poured to dilute hydrochloric acid solution (5%, 500 mL) and stirred for 30 min. The aqueous layer was extracted by EtOAc (3 × 30 mL) and the combined organic phases were washed successively by saturated aqueousNaHCO3, brine and dried (anhydrous MgSO4), The solution was concentrated under reduced pressureto yield 36.5 g (84%) acetate 3, colorless oil. 1H-NMR (300 MHz, CDCl3): δ = 5.37-5.32 (m, 1H,=CH-), 5.10-5.06 (m, 1H, =CH-), 4.59 (d, 2H, J = 7.2 Hz, -CH2O-), 2.12-2.01 (m, 7H, -CH2CH2-,CH3CO-), 1.70 (s, 3H, -CH3), 1.68 (s, 3H, -CH3), 1.60 (s, 3H, -CH3). ESI-MS (m/z): 219.2 (M+Na)+. |
72% | With pyridine |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
In acetonitrile Yield given; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 8 % Spectr. 2: 68% | With scandium tris(trifluoromethanesulfonate) at -20℃; for 2.5h; | |
1: 8% 2: 68% | With scandium tris(trifluoromethanesulfonate) at -20℃; for 2.5h; | |
With trimethylsilyl trifluoromethanesulfonate at -20 - 0℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
88% | With N-iodo-succinimide; tetra-n-butylammonium dihydrogen trifluoride In dichloromethane at 0℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With dilithium tetra(tert-butyl)zincate In toluene at 0℃; for 1h; Inert atmosphere; | General procedure: A typical procedure was as follows. Vinyl acetate (5.0mmol), benzyl alcohol (1.0mmol), and solvent (2.0mL) were added to a glass ampoule which had been degassed and filled with nitrogen. A solution of TBZL (0.1mmol) in THF was added under a nitrogen atmosphere to the ampoule placed in a constant-temperature bath. Then the mixture was kept at 25 or 0°C and stirred. After a prescribed period, the mixture was diluted with CDCl3 and transformed in a NMR tube. Conversion of the reaction was determined by 1H NMR at 400MHz. |
99% | With N,N'-bismesityl-imidazol-2-ylidene In tetrahydrofuran at 20℃; for 1h; | |
99% | In tetrahydrofuran at 20℃; for 1h; |
98% | With 1,3-dichlorotetrabutyldistannoxane at 30℃; for 22h; | |
98% | With 1,3-dichlorotetrabutyldistannoxane at 30℃; for 22h; | |
98% | With di(n-butyl)tin oxide at 30℃; for 24h; | (ii) Acetylation of 2 with vinyl acetate in the presence of Bu2SnO (5) followed by columnchromatography using 10%-moist silica gel To a vinyl acetate solution (5.0 mL) of geraniol (2, 771 mg, 5.0 mmol) was added5 (50.1 mg, 0.20 mmol, 0.04 mol% Sn) at rt, and the mixture was stirred at 30 °C for 24h. After evaporation of the mixture, the crude product was subjected to columnchromatography on 10%-moist silica gel (AcOEt/ hex 5:95) to afford geranyl acetate (3)in a pure form (962 mg, 4.9 mmol, 98%). |
97% | With 2,2'-(phenylimino)bis[ethanol]; diethylzinc In toluene at 20℃; for 4h; | |
97% | With 2,2'-(phenylimino)bis[ethanol]; diethylzinc In hexane; toluene at 20℃; for 4h; | |
94% | With hexamethyltriamido-N-benzylimidophosphate In tetrahydrofuran at 20℃; for 38h; | |
With Pseudomonas cepacia lipase In toluene at 80 - 240℃; Enzymatic reaction; | Geranyl acetate synthesis Geranyl acetate synthesis involves the addition of geraniol (1 mmol) and vinylacetate (4 mmol) in a 10 mL glass reaction vessel of 1.6 cm i.d. with a glass lid. Thereaction mixture was diluted by toluene to make volume of 3 mL. Later on, 50 mg ofimmobilized lipase PCL was added to initiate the reaction and was placed at 55C inorbital shaker with an agitation speed of 140 rpm (Scheme 1). Reaction mass sample10 l was withdrawn periodically and analyzed by using the Perkin Elmer, Clarus-400 gas chromatograph equipped with flame ionizing detector and capillary column.The oven temperature was kept at 80C for 3 min with a rise of 10C min-1up to240C for 30 min. The temperature of the detector and injector was maintained 260and 60C respectively. | |
With Diethyl phosphate; zinc(II) chloride at 70℃; for 5h; | 2; 9 Esterification of geraniol with vinyl acetate catalyzed by diethyl phosphate in the air,At room temperature, add diethyl phosphate (1.54g, 0.01mol),Geraniol (308.50g, 2.0mol) and zinc chloride (0.27g, 2.0mmol),Put the three-necked bottle in the oil bath,The top of the three-necked flask is connected with a 20cm long rectification column (inner diameter 24mm, plate number 6),The rectifying column is filled with triangular spiral packing (3*3),The reflux ratio controller is connected above the distillation column,Receive bottle and vacuum system. Turn on stirring and oil bath heating,When the internal temperature of the reaction solution rises to 70°C,Start dropping vinyl acetate (344.36g, 4.0mol) into the three-necked flask,At the same time, turn on the cooling circulating water at the top of the distillation tower and the reflux ratio controller (reflux ratio 2:1),The dropwise addition of vinyl acetate was completed in 3 hours. During the dropping process,Keep the system at normal pressure, and continuously remove the by-product acetaldehyde from the system,Promote the completion of the esterification reaction. 2 hours after dripping,When acetaldehyde no longer distills off the top of the tower, stop the reaction and sample the tower kettle liquid.GC analysis showed that the conversion rate of geraniol was 99.5%,The selectivity of geranyl acetate is 95.9%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | In N,N-dimethyl-formamide at 100℃; for 40h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With potassium carbonate In methanol at 25℃; for 0.166667h; | |
99% | With methanol at 80℃; for 6h; Inert atmosphere; Schlenk technique; | |
96% | With methanol; oxo[hexa(trifluoroacetato)]tetrazinc for 12h; Reflux; Inert atmosphere; |
92% | With methanol; potassium permanganate; trimethylsulphonium iodide at 25℃; chemoselective reaction; | |
90% | With methanol; potassium permanganate at 25℃; chemoselective reaction; | |
86% | With tris(2,4,6-trimethoxyphenyl)phosphine In methanol at 50℃; for 9h; | |
74% | With acetyl chloride In methanol at 20℃; for 4.5h; | |
70% | With potassium carbonate In methanol at 20℃; for 12h; | |
With sodium hydroxide; sodium tetrahydroborate; zinc 2-ethylhexanoate 1.) THF, 70 deg C, 4 h, 2.) 40 deg, 1 h; Yield given; Multistep reaction; | ||
97 % Chromat. | In tetrahydrofuran; methanol at 40℃; for 24h; | |
With potassium carbonate In methanol | ||
With carbon dioxide In N,N-dimethyl-formamide at 20℃; Electrolysis; | ||
With biocatalyst from Citrus sinensis (L.) Osbeck fresh fruit peel In water at 30℃; for 60h; Enzymatic reaction; | General procedure for the deacetylation reactions General procedure: The experimental setting was a modification of the method proposed by Cossy et al. (2009) in order to avoid the substantial organic material loses due to the formation of heavily viscous slurry as a consequence of the rupture of the vegetable tissues during the mechanical stirring. 20 gr. of the biocatalyst (albedo) obtained from 38 gr of fresh fruit peel, which presumably contains 0.152 mg of active acyl esterase (Pasta et al. 2004) were suspended in sterile (distilled water or Citrate buffer, or Na2HPO4/Na3PO4 at the pH values reported in fig. S1) and the organic substrate (0.75 mmol) solubilized in the minimum amount of DMSO was added to the mixture. Stirring was kept for the time required (see discussion) while keeping the temperature at 40 °C. Afterwards, the biocatalyst was removed by filtration and the mixture was extracted with EtOAc. The organic phase was dried over Na2SO4 and concentrated in vacuo. The residue was purified by FC or preparative MPLC (light ether / EtOAc from 4:1 to 1:4) affording compounds: geraniol 2 (Iwasaki et al. 2010) from geranyl acetate (1); 1-acetoxy-4-hydroxy-2-methylnaphthalene 4 (Huang, 2006) from 1,4-diacetoxy-2-methylnaphthalene 3.Experiments of deacetylation of compound 1 were repeated at different temperatures, reaction times and pH (Fig. S1).In the case of TA as starting material, the organic phase obtained after EtOAc extraction was directly analysed by GC-MS (table S1). | |
With acetyl esterase; water In aq. buffer at 35℃; for 8h; Enzymatic reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 72% 2: 23% | Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With MoO(NtBu)(2,6-iPr2C6H3O)2py In toluene at 20℃; Inert atmosphere; Stage #2: With tert.-butylhydroperoxide In decane; toluene at 90℃; for 4h; Inert atmosphere; | |
1: 59% 2: 22% | With rhodium(II) acetate dimer; oxygen; isobutyraldehyde In acetone at 20℃; | 4.2 General procedure General procedure: A two-neck round bottom flask was charged with Rh2(OAc)4 (4.4 mg, 0.01 mmol), and alkene (1.0 mmol) followed by addition of acetone (3.0 mL). A dry-ice condenser was attached to the flask, then, isobutyraldehyde (274 μL, 3.0 mmol) was added; and a constant flow of oxygen was introduced to the system via an oxygen-filled balloon. Reaction completion was monitored by GC-MS. When the reaction was complete, solvent was removed under reduced pressure and the oily residue was separated by flash chromatography using ether-hexanes solvent mixtures. All epoxide product spectroscopic data were in accord with literature data. |
1: 40% 2: 20% | With Fe(bpmen)(OTf)2; dihydrogen peroxide; acetic acid In acetonitrile at 20℃; |
With Oxone; 2,2,2-Trifluoroacetophenone; sodium carbonate In acetonitrile at 20℃; for 24h; | ||
With 2-Picolinic acid; manganese(II) triflate In acetonitrile at -78℃; for 0.0833333h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
at -5℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With methanesulfonamide; AD-mix-β In water; <i>tert</i>-butyl alcohol at 0℃; for 48h; | |
84% | With AD-mix-α; methanesulfonamide In water; <i>tert</i>-butyl alcohol at 0℃; for 48h; Title compound not separated from byproducts; | |
With methanesulfonamide; water In <i>tert</i>-butyl alcohol at 0℃; for 24h; Inert atmosphere; optical yield given as %ee; |
With methanesulfonamide; water In <i>tert</i>-butyl alcohol at 0℃; for 24h; Inert atmosphere; optical yield given as %ee; | ||
84.5 % ee | With potassium osmate(VI); methanesulfonamide; potassium carbonate; hydroquinidein 1,4-phthalazinediyl diether; potassium hexacyanoferrate(III) In water; <i>tert</i>-butyl alcohol at 20℃; for 48h; Overall yield = 66 %; | (S,E)-6,7-dihydroxy-3,7-dimethyloct-2-enyl acetate (4)[1]: General procedure: To a solution of geranyl acetate 3 (6.2 g, 31.6 mmol) in 380 mL of 1:1 t-BuOH-H2O was added (DHQ)2PHAL (0.24 g, 0.32 mmol), K2OsO4 (0.025 g, 0.06 mmol), K3Fe(CN)6 (31 g, 94.9 mmol), K2CO3 (13.1 g, 94.5 mmol), CH3SO2NH2 (3 g, 31.6 mmol), at room temperature. After stirring for 48 h, the resulting yellow suspension was treated with sodium sulfite (40 g) and stirred for 25 min. After removal of t-BuOH under reduced pressure ,the mixture was extracted with DCM (3 x 100 mL), the combined organic layers were washed with water, and then brine(100 mL), dried over anhydrous Na2SO4, filtered and concentrated to give the crude product which was further purified by silica gel chromatography (PE/EA = 2:1) to give (S,E)-6,7-dihydroxy-3,7-dimethyloct-2-enyl acetate (4) (5 g, 69%) as a colorless oil. Rf = 0.4 (stained by PMA, PE/EA= 2:1). 1H NMR (400 MHz, Chloroform-d) δ 5.39 (tt, J = 7.1, 1.3 Hz, 1H), 4.66 - 4.53 (m, 2H), 3.34 (ddd, J = 10.5, 4.5, 2.0 Hz, 1H), 2.46 - 2.41 (m, 1H), 2.33 (ddd, J = 14.7, 10.0, 5.4 Hz, 1H), 2.20 - 2.08 (m, 2H), 2.06 (s, 3H), 1.75 - 1.69 (m, 3H), 1.67 - 1.56 (m, 1H), 1.45 (dddd, J = 13.8, 10.5, 9.5, 5.3 Hz, 1H), 1.21 (s, 3H), 1.17 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With zirconium(IV) chloride In acetonitrile at 20℃; for 0.166667h; | |
80% | With titanium tetrachloride In dichloromethane at 0 - 25℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 96% 2: 2% | With titanium tetrachloride In dichloromethane at -78℃; for 0.25h; | |
1: 68% 2: 5% | With hydrogenchloride In diethyl ether at -78℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With titanium tetrachloride In dichloromethane at -78℃; Stage #2: With water-d2 at -78 - 0℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With tetrapropylammonium perruthennate; 4 A molecular sieve; 4-methylmorpholine N-oxide In dichloromethane at 20℃; | |
With tetrapropylammonium perruthennate |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With acetyl chloride In ethanol at 30℃; for 0.25h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | Stage #1: bis(dimethylphenylsilyl)zinc In tetrahydrofuran at 0℃; for 0.333333h; Stage #2: 3,7-dimethyl-2E,6-octadien-1-yl acetate In tetrahydrofuran at 0℃; for 1h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | In toluene at 20℃; for 20h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | In toluene at 20℃; for 20h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; N-ethyl-N,N-diisopropylamine In water; isopropyl alcohol at 80℃; for 0.166667h; microwave irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
56% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; N-ethyl-N,N-diisopropylamine In water; isopropyl alcohol at 80℃; for 0.166667h; microwave irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
74% | With dichloro(1,1'-bis(diphenylphosphanyl)ferrocene)palladium(II)*CH2Cl2; N-ethyl-N,N-diisopropylamine In water; isopropyl alcohol at 80℃; for 0.166667h; microwave irradiation; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 81% 2: 19% | In dichloromethane at 0℃; for 24h; Title compound not separated from byproducts.; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With selenium(IV) oxide; urea-hydrogen peroxide In water; isopropyl alcohol at 20℃; for 5h; | |
60% | With tert.-butylhydroperoxide; selenium(IV) oxide In dichloromethane | |
24% | With selenium oxidation In ethanol | 2 (8-methoxy-3,7-dimethyl-dodeca-(2E,6E)-dienyl diphosphate(combination of compound represented by formula (B)) The target compound was synthesized using geraniol as a starting material. Use of pyridine and acetic anhydride in geraniol in anhydrous dichloromethaneAcetylation to give acetate(Compound represented by the following formula (bi)) (yield 95%).then,The acetate8-position carbon in ethanolSelenium oxidation,An aldehyde body (a compound represented by the following formula (bii)) was obtained (yield 24%).Next, the aldehyde is subjected to alkaline hydrolysis with potassium hydroxide.An alcohol (compound represented by the following formula (biii)) was formed (yield 38%).Next, the alcohol is treated with imidazole, tert-butyldiphenylchlorosilane (TBDPS) in anhydrous dichloromethane.The compound shown in the following (biv) was obtained (yield 80%).Then, the compound is reacted with butyllithium in an anhydrous ether to obtain a butyl alcohol (the following formula (bv))Compound represented) (yield 73%).Next, the compound is converted to the sodium salt in anhydrous tetrahydrofuran, followed by the sodiumAdding methyl iodide to the salt and passing the Williamson synthesis,An ether (the compound represented by the following (bvi)) was obtained (yield 95%).Next, the ether is subjected to elimination reaction using tetra-n-ammonium fluoride in anhydrous tetrahydrofuran.An alcohol (a compound represented by the following formula (bvii)) was obtained (yield 87%).Next, N-chlorosuccinimide is used in an anhydrous dichloromethane solvent below -40 ° C.Chlorine substitution with dimethyl sulfide on the primary hydroxyl group to give chloride (described below)(bviii) Compound represented) (yield 92%). Next, the chloride is diphosphorylated with tris(tetra-n-butylammonium) hydrogenated diphosphoric acid in anhydrous acetonitrile to obtain the target product (the compound represented by the following formula (bix), which is represented by the formula (B). Compound) (yield 26%). |
With tert.-butylhydroperoxide; selenium(IV) oxide; salicylic acid In dichloromethane at 0℃; | ||
With tert.-butylhydroperoxide; selenium(IV) oxide | ||
2.142 g | Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With selenium(IV) oxide; ethanol for 1h; Reflux; Stage #2: With manganese(IV) oxide In diethyl ether for 15h; | 12 To a solution of geranyl acetate (compound 29, 7.7 ml, 36 mmol) in EtOH (20 ml), SeO2 (4.34 g, 37.9 mmol) was added at room temperature and refluxed for 1 hour. After returning to room temperature, the reaction mixture was filtered through celite. The filtrate was concentrated and then subjected to silica gel column chromatography (hexane:EtOAc = 1:1) to collect fractions containing an alcohol (compound 30) and an aldehyde (compound 31). After the solvent was distilled off, the residue was dissolved in Et2O (100 ml), to which MnO2 (85% purity, 22.5 g, 220 mmol) was then added and stirred for 15 hours. After the reaction mixture was filtered through celite, the filtrate was washed with sat. aq. NaCl and dried over Na2SO4. After the solvent was distilled off, the residue was purified by silica gel column chromatography (hexane:EtOAc = 4:1) to give the aldehyde (compound 31) (2.142 g, 28%). |
Multi-step reaction with 2 steps 1: triphenylphosphine; ozone / dichloromethane 2: toluene |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
64% | With tert.-butylhydroperoxide; selenium(IV) oxide In decane; dichloromethane at 23℃; for 1.5h; Inert atmosphere; regioselective reaction; | |
55% | Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With selenium(IV) oxide In ethanol at 105℃; for 24h; Inert atmosphere; Stage #2: With sodium tetrahydroborate In diethyl ether; ethanol at 0℃; for 4h; Inert atmosphere; | |
37% | With tert.-butylhydroperoxide; selenium(IV) oxide In decane; dichloromethane at 23℃; for 1.5h; Inert atmosphere; |
33% | With tert.-butylhydroperoxide; selenium(IV) oxide; salicylic acid In water at 20℃; | 2 A solution of salisylic acid (485 mg, 3.5 mmol), Se02 (117 mg, 1.05 mmol) and t- BuOOH (12.5 mL, 70 wt% in water, 87.5 mmol) was stirred at room temperature for 15 minutes. Geraniol acetate (6.86 g, 35.0 mmol) was added and the mixture was stirred at room temperature for 2 nights (1 night is probably enough). The mixture was concentrated in vacuo (T<30°C). Diethyl ether (50 mL) was added and the mixture was washed with 3 M NaOH (3x10 mL, aq), water (3x10 mL) and brine (10 mL). The organic phase was dried (Na2S04), filtered and concentrated in vacuo. Flash chromatography (silica, heptane:EtOAc 80:20, 75:25) afforded 2.4 g (33%) of the product. |
3.4% | With tert.-butylhydroperoxide; selenium(IV) oxide | |
With tert.-butylhydroperoxide; selenium(IV) oxide | ||
With tert.-butylhydroperoxide; selenium(IV) oxide; salicylic acid In dichloromethane | ||
Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With selenium(IV) oxide In ethanol for 1h; Reflux; Stage #2: With sodium tetrahydroborate; ethanol at 0℃; for 1h; | 15 [0241] To a solution of geranyl acetate (compound 29, 1.0 ml, 4.7 mmol) in EtOH (20 ml), SeO2 (602 mg, 5.43 mmol) was added at room temperature and refluxed for 1 hour. After returning to room temperature, the reaction mixture was filtered through celite. The filtrate was concentrated and mixed with EtOH (20 ml), followed by cooling to 0°C. To this mixture, NaBH4 (58 mg, 1.5 mmol) was added and stirred for 1 hour. After addition of 2 M aq. HCl (2 ml), the reaction mixture was stirred for 5 minutes and then poured into H2O (30 ml). After extraction with EtOAc, the combined organic layers were washed with sat. aq. NaCl and dried over Na2SO4. After the solvent was distilled off, the residue was subjected to silica gel column chromatography (hexane:EtOAc = 2:1) to give a primary alcohol (compound 30) as a crude product (1.517 g). | |
With tert.-butylhydroperoxide; selenium(IV) oxide regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With N-chloro-succinimide; selenenyl bromide In dichloromethane at 20℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: 3,7-dimethyl-2E,6-octadien-1-yl acetate With pyridine; ozone In dichloromethane at -20 - -15℃; for 3h; Stage #2: With sodium tetrahydroborate In methanol at 0℃; for 1h; | |
Multi-step reaction with 3 steps 1: 100 percent / mCPBA / CH2Cl2 / 2 h / -20 - 20 °C 2: HIO4*2H2O / diethyl ether; tetrahydrofuran / 0.5 h / 0 °C 3: NaBH4 / ethanol / 1 h / 0 °C | ||
Multi-step reaction with 3 steps 1: 47 percent / K2CO3; K3Fe(CN)6; K2OsO4 / 2-methyl-propan-2-ol; H2O / 72 h / 4 °C 2: 98 percent / aq. NaIO4 / acetone / 0 - 20 °C 3: 99 percent / NaBH4 / methanol / 0 °C |
Multi-step reaction with 3 steps 1: 81 percent / MCPBA / CH2Cl2 / 4 h / 20 °C 2: 71 percent / aq. HIO4 / tetrahydrofuran / 0.5 h / 0 °C 3: 67 percent / NaBH4 / ethanol / 2 h / 0 °C | ||
Multi-step reaction with 2 steps 1: 1.) O3, pyridine, 2.) Me2S / 1.) CH2Cl2, -78 deg C 2: 80 percent / NaBH4, EtOH | ||
Multi-step reaction with 3 steps 1: N-Methyl-morpholine N-oxide monohydrate, osmium tetraoxide / acetone; tetrahydrofuran; H2O / 1). 18 h, room temperature, 2) 12 h, 50 deg C 2: Sodium periodate / dioxane; H2O / 1.5 h / 0 - 5 °C 3: Lithium tri-tert-butoxyaluminium hydride / tetrahydrofuran / 0.17 h / Ambient temperature | ||
Multi-step reaction with 2 steps 1: O3 2: NaBH4 / ethanol |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 46 percent / K3Fe(CN)6; K2CO3; CH3SO2NH2 / AD-mix β / 2-methyl-propan-2-ol; H2O / 144 h / 4 °C 2: 92 percent / p-toluenesulfonic acid hydrate / methanol / 2 h / 20 °C | ||
Multi-step reaction with 2 steps 1: 80 percent / AD-mi-β; H2O; t-BuOH / 15 h / 0 °C 2: 97 percent / (+/-)-10-camphorsulfonic acid / CH2Cl2 / 2 h / 0 °C | ||
Multi-step reaction with 2 steps 1: 70 percent / DHQD-PYDZ ligand; K2OsO4; K3Fe(CN)6 / K2CO3; methanesulfonamide / 2-methyl-propan-2-ol; H2O / 12 h / 4 °C 2: 94 percent / pyridinium p-toluenesulfonate / CH2Cl2 / 1 h / 20 °C |
Multi-step reaction with 2 steps 1: AD-mix-β; methanesulfonamide / <i>tert</i>-butyl alcohol / 24 h / 0 °C 2: toluene-4-sulfonic acid / methanol / 3 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1.1: O3; pyridine / CH2Cl2 / -78 °C 1.2: 66 percent / PPh3 / CH2Cl2 / 4 h / -78 - 20 °C 2.1: 77 percent / PPTS / benzene / 3.5 h / Heating | ||
Multi-step reaction with 3 steps 1: 98 percent / n-CPBA, NaOAc / CH2Cl2 / 2 h / 0 °C 2: HIO4*2H2O / diethyl ether; tetrahydrofuran / 0.5 h / 0 °C 3: p-TsOH / toluene / 5 h / Heating | ||
Multi-step reaction with 2 steps 1: oxidation 2: p-CH3C6H4SO3H |
Multi-step reaction with 3 steps 1: 3-chloro-benzenecarboperoxoic acid / dichloromethane / 4 h / -5 - 0 °C 2: periodic acid dihydrate / diethyl ether; tetrahydrofuran / 5 h / 0 °C 3: toluene-4-sulfonic acid / benzene / 5 h / Reflux |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1.1: O3; pyridine / CH2Cl2 / -78 °C 1.2: 66 percent / PPh3 / CH2Cl2 / 4 h / -78 - 20 °C 2.1: 77 percent / PPTS / benzene / 3.5 h / Heating 3.1: dppf; N(Me)4Br / (Pd(π-allyl)Cl)2 / CH2Cl2; H2O / 2.5 h / 20 °C | ||
Multi-step reaction with 6 steps 1: 98 percent / n-CPBA, NaOAc / CH2Cl2 / 2 h / 0 °C 2: HIO4*2H2O / diethyl ether; tetrahydrofuran / 0.5 h / 0 °C 3: p-TsOH / toluene / 5 h / Heating 4: 65 percent / K2CO3 / methanol / 10 h 5: 97 percent / N-chlorosuccinimide-DMS / CH2Cl2 / 6 h / 0 °C 6: 86 percent / dimethylformamide / 5 h / 0 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1.1: tert-butyl hydroperoxide; SeO2 / CH2Cl2; H2O / 36 h / 20 °C 1.2: 68 percent / NaBH4 / methanol; CH2Cl2; H2O / 0 °C 2.1: 89 percent / Dess-Martin periodinane; pyridine / CH2Cl2 / 0.5 h / 20 °C 3.1: methanol; K2CO3 / 1 h / 0 °C | ||
Multi-step reaction with 2 steps 1: 39 percent / SeO2; water / ethanol / 1 h / Heating 2: 100 percent / KOH; water / ethanol / 1 h / -10 °C | ||
Multi-step reaction with 2 steps 1: 1)SeO2, TBHP, 2) PDC / 1) CH2Cl2, 20 h, RT, 2) CH2Cl2, RT, 1 h 2: 71 percent / NaOMe / methanol / 3 h / Ambient temperature |
Multi-step reaction with 2 steps 1: 40 percent / SeO2, t-BuOOH / toluene / 120 h / Ambient temperature 2: 87 percent / aq. K2CO3 / methanol / 1 h | ||
Multi-step reaction with 2 steps 1: (i) SeO2, EtOH, (ii) MnO2, Et2O, (iii) CuCl2 2: KOH / ethanol / -10 °C | ||
Multi-step reaction with 2 steps 1: selenium(IV) oxide / ethanol / 1 h / Reflux 2: potassium carbonate / methanol / 4 h / 20 °C | ||
Multi-step reaction with 3 steps 1: selenium(IV) oxide / ethanol / 1 h / Reflux 2: manganese(IV) oxide / diethyl ether / 15 h 3: potassium carbonate / methanol / 4 h / 20 °C | ||
Multi-step reaction with 2 steps 1: ethanol 2: potassium hydroxide; water |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 26 steps 1.1: 49 percent / salicylic acid; selenium dioxide; tert-butyl hydroperoxide / CH2Cl2; H2O / 24 h / 20 °C 2.1: 85 percent / triphenylphosphine; N-bromosuccinimide / CH2Cl2 / 2 h / -20 °C 3.1: n-butyl lithium / tetrahydrofuran; hexane / 1.5 h / 0 - 20 °C 3.2: 81 percent / tetrahydrofuran; hexane / 3 h / -20 - 20 °C 4.1: (+)-diisopropyl tartrate; titanium isopropoxide; tert-butyl hydroperoxide / CH2Cl2; decane / -20 °C 5.1: 95 percent / pyridine / CH2Cl2 / 48 h / -10 °C 6.1: perchloric acid / tetrahydrofuran; H2O / 2 h / Heating 6.2: 67 percent / 2,6-lutidine / CH2Cl2 / 1 h / -20 °C 7.1: vanadil acetylacetonate; t-butyl hydroperoxide; pyridinium para-toluenesulfonate / 4 Angstroem molecular sieve / various solvent(s); CH2Cl2; decane / 29 h / 20 °C 8.1: sodium iodide; 18-c-6 / butan-2-one / Heating 8.2: 81 percent / tributyltin hydride; AIBN / toluene / 3 h / Heating 9.1: 93 percent / triethylamine / CH2Cl2 / 3 h / -78 °C 10.1: n-butyl lithium / tetrahydrofuran; hexane / 0.5 h / -78 °C 10.2: tetrahydrofuran; hexane / 0.5 h 11.1: N-methylmorpholine N-oxide / tetrapropylammonium perruthenate / CH2Cl2 / 2 h / 20 °C 12.1: 673 mg / samarium diiodide / ethanol; tetrahydrofuran / 0.5 h / -78 °C 13.1: 86 percent / 2,3-dichloro-5,6-dicyano-1,4-benzoquinone / H2O; CH2Cl2 / 1 h / 0 °C 14.1: 90 percent / samarium diiodide / tetrahydrofuran / 0.5 h / 0 °C 15.1: 4-dimethylaminopyridine / CH2Cl2 16.1: HCl / tetrahydrofuran / 5 h / 0 °C 17.1: 264 mg / sodium hydride / tetrahydrofuran / 0.33 h / 50 °C 18.1: 96 percent / Pd(OH)2 / ethanol; cyclohexane / 12 h / Heating 19.1: 91 percent / N-methylmorpholine N-oxide / tetrapropylammonium perruthenate / CH2Cl2 / 0.5 h / 20 °C 20.1: potassium hexamethyldisilazide / tetrahydrofuran; toluene / 0.5 h 20.2: 85 percent / tetrahydrofuran; toluene / -78 - 20 °C 21.1: 97 percent / 2,3-dichloro-5,6-dicyano-1,4-benzoquinone / H2O; CH2Cl2 / 2 h / 0 °C 22.1: DMSO; oxalyl chloride; Et3N / CH2Cl2 / 0.92 h / -78 °C 23.1: dibutylboron triflate; diisopropylethylamine / CH2Cl2 / 0.5 h / -78 °C 23.2: CH2Cl2 / 3 h / -78 - 20 °C 24.1: 12 mg / pyridine; chromium trioxide / CH2Cl2 / 0.33 h / 20 °C 25.1: 85 percent / HF / H2O; acetonitrile / 3 h / 20 °C 26.1: LiOH / H2O; 1,2-dimethoxy-ethane / 7 h / 80 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With methanesulfonamide; AD-mix-α In <i>tert</i>-butyl alcohol at 0℃; for 24h; enantioselective reaction; | 4.4.1. (R,E)-6,7-Dihydroxy-3,7-dimethyloct-2-en-1-yl acetate ((R)-7) General procedure: AD-mix-b (14 g, 10 mmol) and methanesulfonamide (951 mg,10 mmol) were added to a 1:1 mixture of t-BuOH:H2O (100 mL) andvigorously stirred for 15 min at room temperature. After cooling to0C, geranyl acetate (2.13 mL, 10 mmol) was added, the mixturewas stirred at that temperature for 24 h, then quenched with solidsodium metabisulte (13.5 g). The mixture was extracted severaltimes with dichloromethane and the combined organic layers werewashed with a 10% aq. NaOH solution and brine. The crude productwas puried by column chromatography on silica gel (hexane:ethylacetate 7:3) to afford the diol (R)-7 in 96% yield (2.20 g) as acolorless oil. [a]D25 26.1 (c 0.7, CHCl3), lit.28[a]D23 26.8(c 1.0, CHCl3). Following the same procedure with AD-mix-a, theenantiomeric diol (S)-7 was isolated in 90% yield (2.07 g).[a]D25 23.9 (c 0.9, CHCl3), lit.29[a]D20 25.1 (c 0.7, EtOH).1HNMR (500 MHz, CDCl3) d (ppm): 1.17 (s, 3H); 1.22 (s, 3H); 1.45 (m,1H); 1.62 (m, 1H); 1.73 (s, 3H); 1.91 (br s, 2H); 2.06 (s, 3H); 2.12 (m,1H); 2.32 (m, 1H); 3.45 (dd, J 10.5, 2.0 Hz, 1H) 4.59 (d, J 7.0 Hz,2H); 5.40 (br t, J 7.0 Hz, 1H).13C NMR (100 MHz, CDCl3) d (ppm):16.4; 21.01; 23.2; 26.5; 29.4; 35.6; 61.3; 73.0; 78.0; 118.7; 142.0;171.1. MS (EI): m/z 170 (M- AcOH, 1); 152 (3); 111 (18); 94 (32); 81(27); 68 (72); 59 (100); 43 (73). |
87% | With methanesulfonamide; AD-mix-α In water; <i>tert</i>-butyl alcohol at 0℃; | |
57% | With methanesulfonamide; AD-mix α; water In <i>tert</i>-butyl alcohol at 0 - 4℃; enantioselective reaction; |
Multi-step reaction with 5 steps 1: 1.) SeO2; 2.) NaBH4 / 1.) 96percent ethanol, reflux, 10 h; 2.) ether/methanol (3:1), ice cooling 2: 65 percent / tetraisopropoxy orthotitanate, (+)-tartaric acid dimethylester, t-butylhydroperoxide 3: 90 percent / pyridine / 24 h / 0 °C 4: 1.) NaI; 2.) NaBH3CN / 1.) acetone, reflux, 4.5 h; 2.) THF/HMPT (4:1), 60 deg C, 3 h 5: 78 percent / H2O, conc. H2SO4 / tetrahydrofuran / 30 h / 0 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35% | With sodium hydrogencarbonate; 3-chloro-benzenecarboperoxoic acid In dichloromethane at 0℃; for 2h; | |
Multi-step reaction with 4 steps 1: 1.) SeO2; 2.) NaBH4 / 1.) 96percent ethanol, reflux, 10 h; 2.) ether/methanol (3:1), ice cooling 2: 68 percent / tetraisopropoxy orthotitanate, (-)-tartaric acid dimethylester, t-butylhydroperoxide 3: 90 percent / pyridine / 24 h / 0 °C 4: 1.) NaI; 2.) NaBH3CN / 1.) acetone, reflux, 4.5 h; 2.) THF/HMPT (4:1), 60 deg C, 3 h | ||
Multi-step reaction with 3 steps 1.1: potassium osmate(VI); potassium hexacyanoferrate(III); methanesulfonamide / <i>tert</i>-butyl alcohol; water / 48 h / 20 °C 2.1: pyridine; methanesulfonyl chloride / dichloromethane / 12 h / 0 - 23 °C 2.2: 5 h / 20 °C 3.1: dmap; pyridine / 0 - 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 3 steps 1: 1.) selenium dioxide, 2.) sodium borohydride / 1.) 95percent ethanol, reflux, 1 h 2: 4-dimethylaminopyridine, triethylamine / CH2Cl2 / -20 °C 3: potassium carbonate / methanol / 0 °C | ||
Multi-step reaction with 3 steps 1: 1.) SeO2, 70percent aq. t-BuOOH; 2.) NaBH4 / 1.) CH2Cl2, 4 deg C, 20 h; 2.) EtOH, 0 deg C 2: imidazole / dimethylformamide / 24 h / Ambient temperature 3: 84 percent / K2CO3 / methanol / 1 h / Ambient temperature | ||
Multi-step reaction with 3 steps 1: SeO2 2: Et3N, DMAP 3: K2CO3 / methanol |
Multi-step reaction with 3 steps 1: selenium(IV) oxide; tert.-butylhydroperoxide / dichloromethane / 1.5 h / 20 °C 2: 1H-imidazole / dichloromethane / 16 h / 20 °C 3: potassium carbonate / methanol / 3 h / 20 °C |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Multi-step reaction with 2 steps 1: 1.) selenium dioxide, 2.) sodium borohydride / 1.) 95percent ethanol, reflux, 1 h 2: 4-dimethylaminopyridine, triethylamine / CH2Cl2 / -20 °C | ||
Multi-step reaction with 2 steps 1: 1.) SeO2, 70percent aq. t-BuOOH; 2.) NaBH4 / 1.) CH2Cl2, 4 deg C, 20 h; 2.) EtOH, 0 deg C 2: imidazole / dimethylformamide / 24 h / Ambient temperature | ||
Multi-step reaction with 2 steps 1: SeO2 2: Et3N, DMAP |
Multi-step reaction with 2 steps 1: tert.-butylhydroperoxide; selenium(IV) oxide; benzoic acid / dichloromethane 2: dmap; triethylamine / dichloromethane |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With pyridine; dmap; acetic anhydride | 49 Example 49 Example 49 : Geranyl acetate To 130 g geraniol and 200 mL pyridine at 10°C was added 200 mL acetic anhydride followed by 0.4 g 4-dimethylaminopyridine. After stirring for one hour, the mixture was poured onto crushed ice and diluted with 200 mL n-hexane. The organic layer was separated, washed with 10% hydrochloric acid, 10% aqueous sodium bicarbonate and dried over magnesium sulfate (MgSO4). The extract was evaporated in-vacuo to give the title compound (98%) as a colorless oil. This material was used in the subsequent transformation as obtained. |
96.8% | With acetic acid at 110℃; for 2h; | 6 Examples 1 to 5 General procedure: Take 14.48g of acetic acid and 30.84g geraniol,Evenly mixed into the three bottles,Plus 5g acidic functionalized ionic liquid catalyst I,Heated to reflux mixing,Use diverter to divert water,110 reaction 2h,After cooling with ether extraction,Raffinate for the recovery of the catalyst,Decompression recovery of ether,Distilled geranyl acetate,Yield in Table 1 |
Multi-step reaction with 2 steps 1: pyridine; phosphorus tribromoide |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
35%; 25% | With tert.-butylhydroperoxide; 1-butyl-3-methylimidazolium Tetrafluoroborate;selenium(IV) oxide; 3,4-Dihydroxybenzoic acid; In water; at 40 - 50℃; for 6h;Product distribution / selectivity; | Into a 100 mL flask equipped with a magnetic rotor and a reflux condenser, 50 mg of selenium dioxide, 100 mg of 3,4-dihydroxybenzoic acid, 1 g of 1-butyl-3-methylimidazolium tetrafluoroborate and 0.5 g of 70 wt% aqueous tert-butylhydroperoxide were charged and the mixture was stirred and maintained for 30 minutes at an inner temperature of 40 ºC. After that, 1.58 g of geranyl acetate was added to the mixture, and the resulting mixture was heated to an inner temperature of 50 ºC. To the mixture, 2.2 g of 70 wt% aqueous tert-butylhydroperoxide was added dropwise over 1 hour at the same temperature with stirring. The resulting mixture was stirred to effect the reaction for 5 hours at the same temperature. After completion of the reaction, the reaction mixture was cooled to room temperature. 10 g of n-hexane was added to the reaction mixture and the extracting treatment was carried out to obtain a n-hexane phase and an ionic liquid phase. The ionic liquid phase was extracted two times by n-hexane and obtained n-hexane phase was mixed to the n-hexane phase obtained before to obtain an organic phase containing oxygen-containing compounds. 1.5 g of an ionic liquid phase containing 1-butyl-3-methylimidazolium tetrafluoroborate was obtained.Yield of each component E,E-2,6-dimethyl-2,6-octadiene-1,8-diol-8-acetate: 35 %, E,E-2-formyl-8-acetoxy-6-methyl-2,6-octadiene: 25 %, 33 % of the starting geranyl acetate was remained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | In hexane | R.1 Referential Example 1 Referential Example 1 In 100 ml of n-hexane was dissolved 40 g (0.204 mol) of geranyl acetate, and 17.1 g (0.071 mol) of trichloroisocyanuric acid was added slowly and maintained between -10° C. to 0° C. for six hours. After the reaction, excessive trichloroisocyanuric acid and by-produced isocyanuric acid were removed by filtration. The filtrate was washed with an aqueous sodium hydrogencarbonate solution and water, dried over anhydrous magnesium sulfate, and the solvent was evaporated to yield a crude product. The crude product obtained was purified by silica gel chromatography to provide 6-chloro-3,7-dimethyl-2,7-octadiene-1-acetate (hereinafter, compound (a)) in a yield of 86% in the form of pale yellow oil. 1 H-NMR δ (CDCl3) 1.71 (3H, s), 1.81 (3H, s), 1.90-2.22 (4H, m), 2.05 (3H, s), 4.34 (1H, t, J=7 Hz), 4.59 (2H, d, J=7 Hz), 4.90 (1H, s), 5.01 (1H, s), 5.37 (1H, t, J=7 Hz). |
86% | In hexane | R.1 Reference Example 1 Reference Example 1 40 g (0.204 mol) of Geranyl acetate was dissolved in n-hexane, and 17.1 g (0.071 mol) of trichloroisocyanuric acid was added portionwise and the mixture was kept at -10° C. to 0° C. for 6 hours. After the reaction, excess trichloroisocyanuric acid and a by-product, isocyanuric acid, were filtered off from the reaction system. The filtrate was washed successively with sodium hydrogen carbonate and water and dried over anhydrous magnesium sulfate, and the solvent was distilled off to obtain a crude product. The crude product thus obtained was purified by a column chromatography on a silica gel to give 6-chloro-3,7-dimethyl-2,7-octadiene-1-acetate (hereinafter referred to as Compound (a)) as a pale yellow oil in 86% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | In hexane | R.1 Reference Example 1 Reference Example 1 First, 40 g (0.204 mol) of geranyl acetate was dissolved in 100 ml of n-hexane, to which 17.1 g (0.071 mol) of trichloroisocyanuric acid was slowly' added, and the mixture was kept at -10°C to 0°C for 6 hours. After the reaction, excess trichloroisocyanuric acid and a by-product, isocyanuric acid were removed by filtration. The filtrate was sequentially washed with an aqueous sodium bicarbonate solution and water, dried over anhydrous magnesium sulfate, and then evaporated to remove the solvent, which afforded a crude product. The resulting crude product was purified by silica gel column chromatography, which afforded 6-chloro-3,7-dimethyl-2,7-octadien-1-acetate (hereinafter referred to as compound (f)) as a pale yellow oil in 86% yield. 1H-NMR (CDCl3) δ(ppm): 1.71 (s, 3H), 1.81 (s, 3H), 1.90-2.22 (m, 4H), 2.05 (s, 3H), 4.34 (t, J = 7 Hz, 1H), 4.59 (d, J = 7 Hz, 2H), 4.90 (s, 1H), 5.01 (s, 1H), 5.37 (t, J = 7 Hz, 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | With anilinium hypophosphorous salt; ammonium formate In toluene for 10h; Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With anilinium hypophosphorous salt In toluene Heating; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With Tri-n-octylamine at 125℃; for 1h; Heating / reflux; | 3 Preparation of Geranyl Acetate EXAMPLE 3 Preparation of Geranyl Acetate A reaction flask equipped as in Example 1 is charged with acetic anhydride (600 g, 5.9 mol), DMAP (7.5 g), and tri-n-octylamine (50 g). The mixture is heated to reflux (about 125° C.), and geraniol/nerol mixture (500 g) is added dropwise over about 1 hour. Acetic acid is continuously removed overhead by distillation (200 mm Hg). When GC analysis shows that conversion is complete, residual acetic acid and unreacted acetic anhydride are removed by distillation at 200 mm Hg. Continued distillation at 2 mm Hg provides crude geranyl acetates (640 g, 92% yield) having a purity of about 91%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
95% | With potassium hydroxide; tert-butylammonium hexafluorophosphate(V) In benzene at 15℃; for 6h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With potassium hydroxide; tert-butylammonium hexafluorophosphate(V) In benzene at 15℃; for 6h; |
Tags: 105-87-3 synthesis path| 105-87-3 SDS| 105-87-3 COA| 105-87-3 purity| 105-87-3 application| 105-87-3 NMR| 105-87-3 COA| 105-87-3 structure
[ 10236-16-5 ]
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P304 + P341 | IF INHALED: If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P305 + P351 + P338 | IF IN EYES: Rinse cautiously with water for several minutes. Remove contact lenses, if present and easy to do. Continue rinsing. |
P306 + P360 | IF ON CLOTHING: Rinse Immediately contaminated CLOTHING and SKIN with plenty of water before removing clothes. |
P307 + P311 | IF exposed: call a POISON CENTER or doctor/physician. |
P308 + P313 | IF exposed or concerned: Get medical advice/attention. |
P309 + P311 | IF exposed or if you feel unwell: call a POISON CENTER or doctor/physician. |
P332 + P313 | IF SKIN irritation occurs: Get medical advice/attention. |
P333 + P313 | IF SKIN irritation or rash occurs: Get medical advice/attention. |
P335 + P334 | Brush off loose particles from skin. Immerse in cool water/wrap in wet bandages. |
P337 + P313 | IF eye irritation persists: Get medical advice/attention. |
P342 + P311 | IF experiencing respiratory symptoms: call a POISON CENTER or doctor/physician. |
P370 + P376 | In case of fire: Stop leak if safe to Do so. |
P370 + P378 | In case of fire: |
P370 + P380 | In case of fire: Evacuate area. |
P370 + P380 + P375 | In case of fire: Evacuate area. Fight fire remotely due to the risk of explosion. |
P371 + P380 + P375 | In case of major fire and large quantities: Evacuate area. Fight fire remotely due to the risk of explosion. |
Storage | |
Code | Phrase |
P401 | |
P402 | Store in a dry place. |
P403 | Store in a well-ventilated place. |
P404 | Store in a closed container. |
P405 | Store locked up. |
P406 | Store in corrosive resistant/ container with a resistant inner liner. |
P407 | Maintain air gap between stacks/pallets. |
P410 | Protect from sunlight. |
P411 | |
P412 | Do not expose to temperatures exceeding 50 oC/ 122 oF. |
P413 | |
P420 | Store away from other materials. |
P422 | |
P402 + P404 | Store in a dry place. Store in a closed container. |
P403 + P233 | Store in a well-ventilated place. Keep container tightly closed. |
P403 + P235 | Store in a well-ventilated place. Keep cool. |
P410 + P403 | Protect from sunlight. Store in a well-ventilated place. |
P410 + P412 | Protect from sunlight. Do not expose to temperatures exceeding 50 oC/122oF. |
P411 + P235 | Keep cool. |
Disposal | |
Code | Phrase |
P501 | Dispose of contents/container to ... |
P502 | Refer to manufacturer/supplier for information on recovery/recycling |
Physical hazards | |
Code | Phrase |
H200 | Unstable explosive |
H201 | Explosive; mass explosion hazard |
H202 | Explosive; severe projection hazard |
H203 | Explosive; fire, blast or projection hazard |
H204 | Fire or projection hazard |
H205 | May mass explode in fire |
H220 | Extremely flammable gas |
H221 | Flammable gas |
H222 | Extremely flammable aerosol |
H223 | Flammable aerosol |
H224 | Extremely flammable liquid and vapour |
H225 | Highly flammable liquid and vapour |
H226 | Flammable liquid and vapour |
H227 | Combustible liquid |
H228 | Flammable solid |
H229 | Pressurized container: may burst if heated |
H230 | May react explosively even in the absence of air |
H231 | May react explosively even in the absence of air at elevated pressure and/or temperature |
H240 | Heating may cause an explosion |
H241 | Heating may cause a fire or explosion |
H242 | Heating may cause a fire |
H250 | Catches fire spontaneously if exposed to air |
H251 | Self-heating; may catch fire |
H252 | Self-heating in large quantities; may catch fire |
H260 | In contact with water releases flammable gases which may ignite spontaneously |
H261 | In contact with water releases flammable gas |
H270 | May cause or intensify fire; oxidizer |
H271 | May cause fire or explosion; strong oxidizer |
H272 | May intensify fire; oxidizer |
H280 | Contains gas under pressure; may explode if heated |
H281 | Contains refrigerated gas; may cause cryogenic burns or injury |
H290 | May be corrosive to metals |
Health hazards | |
Code | Phrase |
H300 | Fatal if swallowed |
H301 | Toxic if swallowed |
H302 | Harmful if swallowed |
H303 | May be harmful if swallowed |
H304 | May be fatal if swallowed and enters airways |
H305 | May be harmful if swallowed and enters airways |
H310 | Fatal in contact with skin |
H311 | Toxic in contact with skin |
H312 | Harmful in contact with skin |
H313 | May be harmful in contact with skin |
H314 | Causes severe skin burns and eye damage |
H315 | Causes skin irritation |
H316 | Causes mild skin irritation |
H317 | May cause an allergic skin reaction |
H318 | Causes serious eye damage |
H319 | Causes serious eye irritation |
H320 | Causes eye irritation |
H330 | Fatal if inhaled |
H331 | Toxic if inhaled |
H332 | Harmful if inhaled |
H333 | May be harmful if inhaled |
H334 | May cause allergy or asthma symptoms or breathing difficulties if inhaled |
H335 | May cause respiratory irritation |
H336 | May cause drowsiness or dizziness |
H340 | May cause genetic defects |
H341 | Suspected of causing genetic defects |
H350 | May cause cancer |
H351 | Suspected of causing cancer |
H360 | May damage fertility or the unborn child |
H361 | Suspected of damaging fertility or the unborn child |
H361d | Suspected of damaging the unborn child |
H362 | May cause harm to breast-fed children |
H370 | Causes damage to organs |
H371 | May cause damage to organs |
H372 | Causes damage to organs through prolonged or repeated exposure |
H373 | May cause damage to organs through prolonged or repeated exposure |
Environmental hazards | |
Code | Phrase |
H400 | Very toxic to aquatic life |
H401 | Toxic to aquatic life |
H402 | Harmful to aquatic life |
H410 | Very toxic to aquatic life with long-lasting effects |
H411 | Toxic to aquatic life with long-lasting effects |
H412 | Harmful to aquatic life with long-lasting effects |
H413 | May cause long-lasting harmful effects to aquatic life |
H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
Sorry,this product has been discontinued.
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