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CAS No. : | 766-47-2 | MDL No. : | MFCD03427202 |
Formula : | C9H8 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | MYBSUWNEMXUTAX-UHFFFAOYSA-N |
M.W : | 116.16 | Pubchem ID : | 136598 |
Synonyms : |
|
Num. heavy atoms : | 9 |
Num. arom. heavy atoms : | 6 |
Fraction Csp3 : | 0.11 |
Num. rotatable bonds : | 0 |
Num. H-bond acceptors : | 0.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 39.34 |
TPSA : | 0.0 Ų |
GI absorption : | Low |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | No |
CYP2C9 inhibitor : | No |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -5.21 cm/s |
Log Po/w (iLOGP) : | 2.21 |
Log Po/w (XLOGP3) : | 2.53 |
Log Po/w (WLOGP) : | 2.06 |
Log Po/w (MLOGP) : | 4.08 |
Log Po/w (SILICOS-IT) : | 2.96 |
Consensus Log Po/w : | 2.77 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 2.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -2.65 |
Solubility : | 0.262 mg/ml ; 0.00225 mol/l |
Class : | Soluble |
Log S (Ali) : | -2.18 |
Solubility : | 0.774 mg/ml ; 0.00666 mol/l |
Class : | Soluble |
Log S (SILICOS-IT) : | -2.81 |
Solubility : | 0.179 mg/ml ; 0.00154 mol/l |
Class : | Soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 1.0 |
Synthetic accessibility : | 1.4 |
Signal Word: | Danger | Class: | 3 |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | 3295 |
Hazard Statements: | H225-H315-H319-H335 | Packing Group: | Ⅲ |
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 |
---|---|---|
87% | With anhydrous potassium trimethylsilanolate In dimethyl sulfoxide at 60℃; for 7h; Sealed tube; | 21 2-[(trimethylsilyl)ethynyl]toluene (1 mmol), inorganic base potassium tert-butoxide (sodium) or potassium hydroxide (sodium) or potassium trimethylsilylate (sodium) (0.05 mmol), 2 mL of DMA or DMSO solvent was sequentially added to a 10 mL sealed tube, and the mixture was heated and stirred in a 60°C oil bath for 7 hours. The progress of the reaction was followed by TLC. The reaction was completed and an equivalent of mesitylene or n-undecane was added as a crude product. The exact yield of the product was determined by GC and GC-MS. According to GC and GC-MS, when DMSO is used as a reaction solvent, inorganic base potassium tert-butoxide (sodium) or potassium hydroxide (sodium) or potassium trimethylsilylate (sodium) is used as a catalyst, and the yields of the products are as follows: 59%, 66%, 68%, 76%, 87%, 83%. When DMA was used as the reaction solvent, the inorganic potassium tert-butoxide (sodium) or potassium hydroxide (sodium) or potassium trimethylsilylate (sodium) was used as the catalyst. The yield of the product was: 50%, 58%, respectively. 57%, 69%, 78%, 83%. |
82% | With potassium carbonate In methanol at 20℃; for 3h; | |
80% | With methanol; potassium carbonate at 20℃; |
70% | With potassium carbonate In methanol; dichloromethane for 1h; Inert atmosphere; | |
53% | With N,N,N-tributylbutan-1-aminium fluoride In tetrahydrofuran at 0℃; for 1h; | |
29% | With potassium fluoride In methanol | D Preparation of 1-ethynyl-2- methylbenzene; general procedure D The TMS group was removed by KF (2.0 g, [35] mmol) in MeOH (10 ml) to afford a [310] mg (29% in 2 steps) of 1-ethynyl-2- methylbenzene as brown oil. |
23% | Stage #1: trimethyl(o-tolylethynyl)silane With N,N,N-tributylbutan-1-aminium fluoride In tetrahydrofuran at 0℃; for 0.5h; Inert atmosphere; Stage #2: With ammonia hydrochloride Inert atmosphere; | |
(alkaline hydrolysis); | ||
2.00 g | With N,N,N-tributylbutan-1-aminium fluoride In tetrahydrofuran; lithium hydroxide monohydrate at 20℃; | |
With potassium carbonate In methanol | ||
Stage #1: trimethyl(o-tolylethynyl)silane With methanol; potassium hydroxide at 0℃; Stage #2: With hydrogenchloride; lithium hydroxide monohydrate In methanol | B1 Potassium hydroxide (10Og, l.δmol) added in 4 portions to a stirred solution of trimethyl-(2-methylphenyl)ethynylsilane (114.Og, O.lmol) in methanol (400ml) at 00C. The mixture was stirred at 00C until the reaction was complete (by tic 1:1 ethyl acetate:hexane). The mixture was neutralised by the addition of 10% hydrochloric acid and the product was extracted into dichloromethane (2xl50ml). The combined extracts were dried (MgSO4) and evaporated in vacuo. The residual oil was purified by short path distillation (Kugelrohr) to give l-ethynyl-2- methylbenzene (52.03g) as a clear oil. B.pt. 45°C/12mBar. 250 MHz 1H-NMR(CDCl3) δ (ppm): 2.35 (s, 3H) (ArCH3), 3.2 (s, IH) (CH), 7.0-7.2 (m, 3H) (3 x ArH), 7.4 (m, IH) (ArH); GC purity 98%, GC retention time 7.94min. | |
With sodium hydroxide In tetrahydrofuran; methanol; lithium hydroxide monohydrate at 20℃; for 0.5h; | ||
With N,N,N-tributylbutan-1-aminium fluoride In tetrahydrofuran at -78 - 20℃; Inert atmosphere; | ||
With methanol; potassium carbonate In dichloromethane at 20℃; for 12h; Inert atmosphere; Schlenk technique; | ||
1.96 g | With N,N,N-tributylbutan-1-aminium fluoride In tetrahydrofuran at 0 - 20℃; for 0.5h; | |
With potassium fluoride at 20℃; for 16h; | One-Pot Sonogashira-Glaser Cyclization/Synthesis of Thiophenes; General procedure: A mixture of a (hetero)aryl iodide 1 (2.00 mmol), Pd(PPh3)2Cl2(28.1 mg, 0.04 mmol, 2 mol%), and CuCl (7.92 mg, 0.08 mmol, 4mol%) was dissolved in DMSO (1.00 mL) in a 8 mL microwavevessel equipped with a stirring bar and a septum and was degassedwith N2 for 5 min. After the addition of TMSA (0.42 mL,3.00 mmol) and anhydrous Et3N (0.55 mL, 4.00 mmol), the solutionwas stirred at r.t. for 1 h. Then, KF (232 mg, 4.00 mmol) wasadded and the reaction mixture was vigorously stirred under air inthe open reaction vessel at r.t. for 16 h. After the addition of themethanethiol 2 (or 6, 8) (1.20 mmol, 0.6 equiv), KOH (224 mg,4 mmol), and DMSO (1.00 mL), the mixture was heated in the microwavecavity at 130°C for 1 h. After cooling to r.t., the solventswere removed under reduced pressure. The residue was absorbed onCelite and purified by column chromatography on silica gel with n-hexane or n-hexane-THF (100:1) as eluent. The experimental detailsare shown in Table 2. | |
With potassium fluoride In tetrahydrofuran; methanol at 20℃; for 1h; Inert atmosphere; | ||
With potassium carbonate In methanol | ||
With potassium carbonate In methanol at 20℃; for 2h; | ||
With copper (I) iodide; hydrofluorosilicic acid; N-ethyl-N,N-diisopropylamine In tetrahydrofuran; lithium hydroxide monohydrate at 60℃; for 2h; | ||
With potassium carbonate In methanol at 20℃; | ||
With potassium fluoride In methanol at 20℃; for 24h; Sealed tube; | ||
With N,N,N-tributylbutan-1-aminium fluoride In tetrahydrofuran at 20℃; for 0.5h; | General procedure for the synthesis of substituted acetylenes S15-S26 General procedure: To a suspension of the required aryl iodide (1.0 mmol), Pd(PPh3)2Cl2 (70.2 mg, 0.1 mmol) and CuI (38.1 mg, 0.2 mmol) in dry THF (20 mL) under argon was added TEA (202.4 mg, 2.0 mmol) and trimethylsilyl acetylene (147.3 mg, 1.5 mmol). The resulting mixture was stirred at rt overnight and then the catalyst was filtered. The filtrate was added TBAF (1M in THF, 1.5 mL) and stirred at rt for 30 min. The reaction was quenched with water (10 mL) and extracted with ethyl acetate. The organic phase was washed with brine, dried over Na2SO4, and reduced to dryness. The residue was purified on silica gel with petroleum ether to afford the corresponding substituted acetylene 6. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | Stage #1: 1-ethynyl-2-methylbenzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Stage #2: methyl iodide In tetrahydrofuran; hexane at -78 - 20℃; for 24h; | 1 Synthesis of l-methyl-2-(prop-l-yn-l-yl)benzene (36) To a solution of 2-ethynyltoluene (1.6 mL, 12.91 mmol) in anhydrous THF (30 mL) was added dropwise a solution of n -butyl lithium (2.5 M in hexanes, 7.75 mL, 19.4 mmol) at -78°C over a period of 20 minutes. After stirring at this temperature for one hour, methyl iodide (1.2 mL, 19.4 mmol) was added dropwise and the reaction mixture was allowed to warm to room temperature. After stirring for 24 hours, the reaction was quenched by the addition of a saturated solution of sodium thiosulfate (20 mL). The organic phase was separated and the aqueous phase was extracted with iso-hexane (2 x 30 mL). The combined organic extracts were dried (Na2SO4), filtered and evaporated to give l-methyl-2-(prop-l-yn-l-yl)benzene (36) as a pale yellow liquid.[00251] Yield 1.7 g (quant).1H NMR (400 MHz, CDCl3) δ 7.35 (d, J=7.3 Hz, 1H), 7.16 (d, J=4.0 Hz, 2H), 7.14 - 7.07 (m, 1H), 2.41 (s, 3H), 2.09 (s, 3H). |
85% | Stage #1: 1-ethynyl-2-methylbenzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Glovebox; Inert atmosphere; Stage #2: methyl iodide In tetrahydrofuran; hexane at -78 - 20℃; for 2.5h; Glovebox; Inert atmosphere; | |
With lithium; ferric nitrate 1.) liq.NH3, HMPA, 30 min; 2.) 6 h; Yield given. Multistep reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
1: 68% 2: 14% | With [(Me3P)3Ru(-OH)3Ru(PMe3)3]+[OPh]-*(HOPh)0.5 at 100℃; for 2h; Inert atmosphere; Schlenk technique; | 4.2.7. 2-Methylphenylacetylene (2g) 2g (116.5 mg, 1.00 mmol) was treated by 1·(HOPh)0.5(4.3 mg, 0.0051 mmol) at 100C for 2 h to give (E)-1,4-bis(2-methylphenyl)but-3-en-1-yne (E-3 g) and(Z)-1,4-bis(2-methylphenyl)but-3-en-1-yne (Z-3 g) in 68% and14% yields, respectively. These products were characterized by GC,GC-MS and NMR. E-3 g:1H NMR (CDCl3): 2.39 (s, 3H, Me), 2.47(s, 3H, Me), 6.33 (d, J = 16 Hz, 1H, =CH), 7.10-7.23 (m, 6H C6H4), 7.26(d, J = 16 Hz, 1H, =CH), 7.44 (d, J = 7 Hz, 1H, C6H4), 7.48-7.55 (m, 1H,C6H4). Z-3 g:1H NMR (CDCl3): 2.34 (s, 3H, Me), 2.39 (overlappedwith the signal for E-3 g, Me), 6.00 (d, J = 12 Hz, 1H, =CH), 6.88 (d,J = 12 Hz, 1H, =CH), 7.1-7.4 (m, overlapped with resonances forE-3 g, C6H4). |
In toluene at 120℃; for 48h; | ||
With bis(tricyclohexylphosphine)benzylidene ruthenium (IV) dichloride; sodium lauryl sulfate In water monomer; toluene at 50℃; for 15h; optical yield given as %de; |
64 % de | With chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II) In tetrahydrofuran at 20℃; for 24h; Inert atmosphere; Schlenk technique; Overall yield = 50 %; | |
18 % de | With [CoBr2(TriPhos)]; zinc(II) iodide; zinc powder In acetonitrile at 0 - 20℃; for 24h; Inert atmosphere; Schlenk technique; Overall yield = 46 percent; Overall yield = 53 mg; diastereoselective reaction; | |
85.859 % de | With 1,3-bis(2,4,6-trimethylphenyl)-2-imidazolidinylidene-dichloro(phenylmethylene)-(tricyclohexyl-phosphine)ruthenium; tricyclohexylphosphine In neat (no solvent) at 120℃; for 2h; Inert atmosphere; Schlenk technique; Overall yield = 96 percent; | |
With C30H55N2OSi2Y In hexane at 20 - 80℃; for 12h; Inert atmosphere; Optical yield = 88 percent de; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With N-Bromosuccinimide; silver nitrate In acetone at 25℃; for 1h; | |
83% | With N-Bromosuccinimide; silver nitrate In acetone at 25℃; for 1h; | |
83% | With N-Bromosuccinimide; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) (2:1) toluene adduct In dichloromethane for 24h; Reflux; |
With N-Bromosuccinimide; silver nitrate In acetone at 20℃; | ||
With N-Bromosuccinimide; silver nitrate In acetone at 20℃; Inert atmosphere; | ||
With N-Bromosuccinimide; silver nitrate In acetone at 20℃; for 2h; Inert atmosphere; | ||
With N-Bromosuccinimide; silver nitrate In acetone at 23℃; for 5h; Inert atmosphere; Darkness; | ||
With N-Bromosuccinimide; silver nitrate In acetone at 25℃; for 3h; Inert atmosphere; | ||
With N-Bromosuccinimide; silver nitrate In acetone at 20℃; for 3h; | ||
With N-Bromosuccinimide; silver nitrate In acetone at 20℃; for 3h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With nitrogen; triphenylphosphine;palladium diacetate; copper(I) iodide; In dichloromethane; triethylamine; | a) Preparation of methyl 2-(2-methylphenyl)-ethynylphenylglyoxylate O-methyloxime (European Patent 253,213, No. 136) 300 mg of palladium(II) acetate, 1.5 g of triphenylphosphine and 100 mg of copper(I) iodide and 11 g (0.095 mol) of 2-methylphenylacetylene are added to a solution of 10 g (0.041 mol) of <strong>[122394-38-1]methyl 2-bromophenylglyoxylate</strong> in 50 ml of triethylamine. Nitrogen is passed through the solution for 30 minutes, after which the solution is heated for 3 hours at 80 C. After cooling, methylene chloride is added and the solution is washed with water. The organic phase is dried and evaporated down. 16.5 g of methyl 2-(2-methylphenyl)-ethynylphenylglyoxylate remain as a black oil. 1 H-NMR (CDCl3 /TMS): delta=2.53 (s, 3H, CH3); 3.81 (s, 3H, OCH3); 7.13-7.88 ppm (m, 8H, aryl). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With triethylamine;bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triphenylphosphine; In N,N-dimethyl-formamide; at 100℃; for 0.333333h;Microwave irradiation; | A mixture of l-ethynyl-2-methylbenzene (0.53g, 4.6mmol), 5-bromo-2- methylsulfanylpyrimidine-4-carboxylic acid methyl ester (l.Og, 3.8mmol), triethylamine (2.5ml), triphenylphosphine (0.125g, 0.48mmol), copper (I) iodide (0.025g, 0.13mmol), fostriphenyphosphinepalladium (II) dichloride (O.lOg, 0.14mmol) and dimethylformamide (ImI) was stirred in a heavy- walled Smith process vial and irradiated with microwaves to maintain 1000C for 20min. The cooled mixture was diluted with dichloromethane (20ml) and washed with 5% hydrochloric acid (20ml), water (20ml), saturated aqueous sodium hydrogencarbonate solution (20ml) and water (20ml) then dried (MgSO/i) and evaporated in vacuo. The residual oil was purified by flash column chromatography over silica using a 1:4 mixture of hexane and dichloromethane as eluant.Appropriate fractions were combined and the solvents removed in vacuo to give 2- methylsulfanyl-5-(2-methylphenyl)ethynylpyrimidine-4-carboxylic acid methyl ester (0.9g) as an orange oil. 250 MHz 1H-NMR (CDCl3) delta (ppm): 2.45 (s, 3H) (ArCH3), 2.55 (s, 3H) (-SCH3), 3.95 (s, 3H) (CO2CH3), 7.05-7.25 (m, 3H) (3 x ArH), 7.45 (m, IH) (ArH), 8.7 (s, IH) (ArH); m/z (M+H)+- 299, HPLC purity 96%, HPLC retention time 4.15 min. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | In diethylamine at 60℃; for 12h; | 4.4a A mixture of 6-lodo-2H-chromene-8-carboxylic acid methyl ester (500 mg), 1-Ethynyl-2- methyl-benzene (0.4 ml_), Pd(PPh3)2CI2 (11 mg) and CuI (5 mg) in diethylamine (10 mL) was stirred at 6O0C for 12 hours. The solvent was distilled off and the residue was extracted with water / ethyl acetate. The solvent of the organic phase was evaporated and the title compound was obtained after flash chromatography in 91% yield (440 mg). 1H- NMR (DMSOd6): 7.85 d (J = 2.1 Hz1 1 H); 7.51 d (J = 7.4 Hz1 1 H); 7.28 m (3H); 7.23 m (1 H); 6.45 m (1 H); 5.93 m (1 H); 5.03 m (2H); 3.94 s (3H); 2.55 s (3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With 1,4-diaza-bicyclo[2.2.2]octane; copper(l) iodide for 0.333333h; zirconia vibration ball mill; neat (no solvent); | |
98% | With 1,4-diaza-bicyclo[2.2.2]octane; [AuIII2(μ-OH)2(OH)4]0.5[AuIII2Cl6PdII2(NH3)6(4,4′-((2-(2-(methylthio)ethoxy)-1,3-phenylene)bis(ethyne-2,1-diyl))dipyridine)2]0.5[PdII2(μ-OH2)(NH3)6]0.5{NiII4[CuII2(Me3Ph(-N=CO-COO)2)2]3}·37H2O In ethyl acetate at 20℃; for 14h; | |
98% | With 1,4-diaza-bicyclo[2.2.2]octane; [AuIII2(μ-OH)2(OH)4]0.5[AuIII2Cl6PdII2(NH3)6(4,4′-((2-(2-(methylthio)ethoxy)-1,3-phenylene)bis(ethyne-2,1-diyl))dipyridine)2]0.5[PdII2(μ-OH2)(NH3)6]0.5{NiII4[CuII2(N,N'-2,4,6-trimethyl-1,3-phenylenebis(oxamate))2]3}·37H2O In ethyl acetate at 20℃; for 14h; |
97% | With sodium acetate; silver sulfate In dimethyl sulfoxide at 90℃; for 12h; | 6.1 Typical experimental procedure for homocoupling of alkynes General procedure: A mixture of alkyne 1 (0.2 mmol), nano-Pd (0.1 mol% Pd), Ag2SO4(30 mol%), NaOAc (1 equiv), and DMSO (1 mL) was stirred at 90 oC until complete consumption of starting material as judged by TLC. After the mixture was filtered and evaporated, the residue was purified by flash column chromatography to afford the product 2 (petroleum ether or petroleum ether/ethyl acetate). |
97% | With copper(II) choride dihydrate; N,N,N,N,-tetramethylethylenediamine; oxygen In dichloromethane at 20℃; | |
96% | With piperidine In toluene at 60℃; for 24h; | General procedure for the aerobic oxidative homocoupling of terminal alkynes: General procedure: A mixture ofcatalyst (PS-TEDETA-CuSO4, 0.05 mmol of Cu), terminal alkyne (0.5 mmol) and piperidine (0.5mmol) in toluene (1.0 mL) was stirred at 60 oC for 24-48 h under air. After cooling, the mixture wasfiltered, and the residue was washed by dichloromethane (2 mL x3). The combined organic phaseswere concentrated in vacuo and the crude products were purified by column chromatography(hexane/AcOEt) to give the corresponding 1,3-diynes. |
96% | With copper(l) iodide; 4,7-bis(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)-1,10-phenanthroline; oxygen In water at 80℃; for 6h; Schlenk technique; Green chemistry; | |
91% | With [Pd(triphenylphosphine)(allyl)(chloride)]; sodium acetate In water; acetone at 25℃; for 25h; Green chemistry; | |
90% | With N,N,N,N,-tetramethylethylenediamine; oxygen; 1,8-diazabicyclo[5.4.0]undec-7-ene; copper(l) chloride In 1,1,1,3,3-pentafluorobutane at 20℃; for 2.5h; | |
90% | With 1,10-Phenanthroline; tetrabutylammonium acetate; acetic acid In acetonitrile at 20℃; Electrochemical reaction; | |
89% | With copper(II) nitrate In dimethyl sulfoxide at 100℃; for 4h; Schlenk technique; Sealed tube; | |
88% | With piperidine; copper(l) chloride In toluene at 60℃; for 5h; | |
86% | With C40H58Cl2N2O4P2Pd; caesium carbonate; silver nitrate In water; butan-1-ol at 60℃; for 24h; | 3.2. General Experimental Procedure for the Homocoupling Reaction of Various Aromatic Alkynes General procedure: All reactions were carried out under aerobic conditions. A mixture of aromatic alkyne (1.0 mmol), AgNO3 (0.075 mmol), Cs2CO3 (1.0 mmol), catalyst compound 1 (0.5 mol %), and n-butyl alcohol/H2O (in 1:2 proportion, 3 mL) was stirred at 60 °C for 24 h and then extracted three times with ethyl acetate (3 x 15 mL). The combined organic phase was dried with MgSO4, filtrated, and then solvent was removed on a rotary evaporator. The product was isolated by thin-layer chromatography. The purified products were identified by 1H-NMR and 13C-NMR spectroscopy (Figures S1-S10). |
86% | With piperidine; iodine In water at 100℃; for 12h; regioselective reaction; | General experimental procedure for the synthesis of 1,3-diynes 2a-p using terminal acetylenes 1a-p General procedure: A 10 mL reaction vial was charged with a terminal acetylenes 1a-p (1.0 mmol), piperidine (3.0 mmol), H2O (1 mL) and 30 mol% molecular iodine. The reaction vial was then heated at 100 °C for 12 h. After completion of the reaction (progress was monitored by TLC; SiO2, Hexane/EtOAc = 9.5:0.5), the mixture was diluted with ethyl acetate (15 mL) and water (20 mL) and extracted with ethyl acetate (3 × 10 mL). The combined organic layer was washed with brine (3 × 10 mL) and dried over anhydrous Na2SO4. Solvent was removed under reduced pressure and the remaining residue was purified by column chromatography over silica gel using hexane / ethyl acetate (9.5:0.5) as an eluent to obtain the desired products 2a-p in high yields. |
84% | With (triphenylphosphine)gold(I) chloride; [bis(acetoxy)iodo]benzene; potassium carbonate In 1,2-dichloro-ethane at 60℃; for 8h; Inert atmosphere; | |
84% | With Co(salen)complex; N,N'-di-tert-butyldiaziridinone In ethyl acetate at 80℃; for 6h; Schlenk technique; Inert atmosphere; | Cobalt-Catalyzed Homocoupling Reaction; General Procedure General procedure: To a flame-dried Schlenk tube with a stir bar was added Co(salen)complex 4 (10 mol%). The contents were evacuated and backfilledwith N2 (3 ×). Di-tert-butyldiaziridinone (2; 0.3 mmol) and alkyne(0.2 mmol) were added via microinjection syringe dissolved in anhydEtOAc (0.2 M). The mixture was stirred at 80 °C (oil bath). When thereaction was complete (TLC monitoring), the mixture was directlyconcentrated by rotary evaporation. The coupling products wereisolated by column chromatography (silica gel, typically 0-30%EtOAc/PE) |
81% | With copper(l) iodide; oxygen; benzylamine In neat (no solvent) at 20℃; for 12h; Green chemistry; | |
78% | With potassium acetate; silver nitrate; triphenylphosphine In N,N-dimethyl-formamide at 80℃; for 3h; | |
70% | With C38H28O4P2Pd; silver nitrate; triethylamine In tetrahydrofuran; water at 60℃; for 10h; | Typical experimental procedure for the homocoupling reactions of terminal alkynes. General procedure: All homocoupling reactions of aromatic terminal alkyneswere carried out under air. A mixture of aromatic terminal alkyne (1.0 mmol), NEt3 (1.0 mmol) and P-O coordinatedcyclopalladated complex 1 (0.005 mmol)/AgNO3 (0.5 mmol) inTHF:H2O (in 4:1 proportion, 2.5 mL) was allowed to react at60°C. The reaction progress was analyzed by GLC. The mixturewas added brine (4 mL) and extracted three times with ethylacetate (3 × 15 mL), dried over Na2SO4, concentrated in vacuoand purifed by thin layer chromatography. The purifed products were identifed by 1H-NMR and 13C-NMR spectroscopy.The Supplemental Materials presents sample 1H and 13C NMRspectra of the diyne products (Figures S1-S24). |
68% | With 4,4’‐bis(trimethylammoniummethyl)‐2,2’‐bipyridine; copper(ll) sulfate pentahydrate; iodine; potassium acetate In water at 120℃; for 24h; | |
56% | With copper(I) oxide; tetrabutylammomium bromide; oxygen; sodium hydroxide In water at 80℃; for 15h; Green chemistry; | |
55% | With copper(l) iodide; iodine; sodium carbonate In N,N-dimethyl-formamide at 80℃; for 4h; Schlenk technique; | |
37% | With 4,4’‐bis(trimethylammoniummethyl)‐2,2’‐bipyridine; copper(l) iodide; diamminedichloropalladium(II); tetrabutylammomium bromide; iodine; triethylamine In water at 20℃; for 48h; | |
20% | With piperidine; copper(l) chloride In toluene at 60℃; | |
95 %Chromat. | With oxygen In benzonitrile at 99.84℃; for 3h; | |
99 %Chromat. | With oxygen In toluene at 100℃; for 0.5h; | |
99 %Chromat. | With oxygen In toluene at 100℃; | |
95 %Chromat. | With oxygen In benzonitrile at 100℃; for 3h; | |
Multi-step reaction with 2 steps 1: ethylmagnesium bromide / tetrahydrofuran; diethyl ether / 1 h / 0 °C / Inert atmosphere 2: iron(III) chloride; 1,2-Diiodoethane / tetrahydrofuran; diethyl ether / 0.33 h / 0 °C / Ionic liquid; Inert atmosphere | ||
With copper(l) chloride In dimethyl sulfoxide at 90℃; for 8h; | ||
78 %Chromat. | With piperidine In toluene at 100℃; for 2h; | |
90 %Chromat. | With Au/C; oxygen at 170℃; for 18h; | 2.2.2 Initial rate measurements General procedure: Initial rates were calculated from the slope of the first-order kinetic curves of the homocoupling of ortho-tolylacetylene under different pressures of oxygen or at different concentrations of alkyne. The points of the kinetic curves were obtained from independent batch experiments by stopping the reaction at different reaction times. For that, the solid catalyst (Au/C or Au/CeO2: 41mg, Au/ZnO: 65mg; 2mol% Au) was placed in a thick double-walled 2.5-ml glass reactor equipped with a magnetic stirrer. Then, 1,3-dichlorobenzene (0.5ml) and the corresponding amount of ortho-tolylacetylene were added and the vial capped with the pressure system. Neat molecular oxygen gas was loaded through a needle until the manometer indicated the corresponding pressure. Then, the reactor was magnetically stirred in a pre-heated oil bath at 170°C for the desired time. After this time, the reactor was cooled with water and the gas released. Diethyl ether (1ml) was added and the whole mixture was filtered and submitted to GC and GC-MS analysis after dodecane (22μl, 0.1mmol) was added as an external standard. The yield of homocoupling of ortho-tolylacetylene was plotted versus time and the slope at low yields gives the initial rate in h-1. |
Multi-step reaction with 2 steps 1.1: n-butyllithium / tetrahydrofuran; hexane / 3 h / -78 °C / Inert atmosphere 1.2: 2 h / -78 °C / Inert atmosphere 2.1: copper(l) chloride; [2,2]bipyridinyl / N,N-dimethyl-formamide / 6 h / 25 °C | ||
With copper(II) choride dihydrate; triethylamine In methanol at 25℃; for 3h; Irradiation; | 2.1-2.5 Example 2 Step 1: Add 0.05mmol CuCl2 · 2H2O to 10mL methanol to form a light blue transparent solution;Step 2: Under the condition of continuous stirring, 2 mmol of Et3N was added dropwise to the above solution, a blue-black precipitate was formed, and a suspension 2 was formed;Step 3: Add 1 mmol to Suspension 2 with continuous stirring2-methylphenylacetylene, the blue-black precipitate turns green, forming a green suspension 3;Step 4: Under the condition of continuous stirring, the suspension 3 is irradiated with sunlight and stirred for 3 hours.Step 5: The reaction solution is filtered, rotated,Separation by column (column chromatography) and other steps,Then, 1,4-bis (2-tolyl) -1,3-butadiyne can be obtained;The catalyst used in step 1 is a Cu (II) salt. The reaction temperature involved in step 4 is room temperature, usually room temperature is 25 degrees. The reaction pressure involved in step 4 is a standard atmospheric pressure.The reaction environment involved in step 4 is air. | |
74 %Spectr. | With copper(l) chloride In water; dimethyl sulfoxide at 20℃; for 12h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With bis(N,N'-bis(2,6-diisopropylphenyl)imidazol-2-ylidene)palladium(0); tris(2,6-dimethoxyphenyl)phosphine In toluene at 60℃; for 1.5h; Inert atmosphere; stereoselective reaction; | |
81% | With C48H60N4Pd; tris(2,6-dimethoxyphenyl)phosphine In toluene at 60℃; for 1.5h; Inert atmosphere; Glovebox; Schlenk technique; stereoselective reaction; | |
70% | With [CoBr2(dppp)]; triphenylphosphine; zinc In acetonitrile at 0 - 20℃; for 18h; Inert atmosphere; Schlenk technique; diastereoselective reaction; |
69% | With Wilkinson's catalyst; sodium dodecyl-sulfate In water; toluene at 50℃; for 15h; | |
0.054 g | With [ruthenium(II)(η6-1-methyl-4-isopropyl-benzene)(chloride)(μ-chloride)]2; acetic acid In tetrahydrofuran; methanol; water at 20℃; for 24h; Inert atmosphere; optical yield given as %de; stereoselective reaction; | |
93 %Spectr. | With C28H30CoNOP In tetrahydrofuran at 40℃; for 12h; Inert atmosphere; Glovebox; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 65℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With C17H32Cl2N4OPd; potassium carbonate; In ethanol; at 80℃; for 1h; | General procedure: K2CO3 (2.5 × 10-4 mol, 2.5 equiv), aryl iodide (1.0 × 10-4 mol, 1.0 equiv), and alkyne (1.5 × 10-4 mol, 1.5 equiv) were mixed in a 10-mL vial, followed by addition of a solution of the selected catalyst (1 × 10-8 mol) in EtOH (1 mL). The vial was placed in a preheated oil bath at 80 C and stirred for 1 h. After cooling to 20-25 C, the reaction mixture was evaporated to dryness under a stream of dinitrogen followed by addition of 1.0 equiv of 1,2-dimethoxyethane as NMR internal standard, and extraction of the reaction mixture with three 0.20-mL portions of CDCl3. All fractions were joined and analyzed by 1H NMR spectroscopy. The product peak assignments were based on the authentic samples or on published dat, whereas quantifications were performed upon integration of the selected peak of the product relatively to the peak of the standard. |
With C23H20Cl4N4OPd; potassium carbonate; In ethanol; at 80℃; for 4h; | General procedure: Selected base (1.5×10-4 mol, 1.5 equivs), aryl iodide (1.0×10-4 mol, 1.0 equiv) and terminal alkyne (1.0×10-4 mol, 1.0 equivs) were mixed in a 10-mL vial, followed by addition of a solution of the selected catalyst (1×10-8 mol) in EtOH (1 mL). The vial was placed in a pre heated oil bath at 80 C and stirred for 4 h. After cooling to ca. 25 C, the reaction mixture was evaporated to dryness under a stream of dinitrogen followed by addition of 1.0 equivof 1,2-dimethoxyethane (NMR internal standard), and extraction of the reaction mixture with three 0.20 mL portions of CDCl3. All fractions were joined and analyzed by 1H NMR spectroscopy. The product peak assignments were based on authentic samplesor on published data [56,62-68] (several sources were used for published compounds), while the structure of two new products,i.e. 3,4-dimethoxy-5-(phenylethynyl)benzaldehyde (derived from the coupling of 3-iodo-4,5-dimethoxybenzaldehyde with phenylacetylene) and 1-fluoro-2-[(2-methylphenyl)ethynyl]benzene (prepared from 2-fluorophenylacetylene and 2-iodotoluene were undoubtedly established using NMR spectroscopy, MS and elemental analyses (see Supplementary data). Quantifications were performed upon integration of the selected peak of the product in the 1H NMR relatively to the peak of the standard. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | Stage #1: 4-(3-iodo-benzyl)-piperazine-1-carboxylic acid benzo[d]isoxazol-3-ylamide With triethylamine In tetrahydrofuran for 0.25h; Stage #2: 1-ethynyl-2-methylbenzene In tetrahydrofuran at 20℃; for 0.166667h; | 63.C To a solution of Pd(PPh3)2Cl2 (7.2 mg) inTHF/Et3N (1 ml_ each) was added 4-(3-iodo-benzyl)-piperazine-1-carboxylic acid benzo[d]isoxazol-3-ylamide (100.0 mg). The solution was degassed for 15 min, then copper(l) iodide (4.6 mg) and 2-ethynyltoluene (37.8 mg) were added. The reaction mixture was stirred at rt for 10 min, then poured into water and extracted with EtOAc (3x). The organic layers were combined, washed with NH4OH, dried (Na2SO4), and concentrated. The crude residue was purified (FCC) to afford the title compound (89.3 mg, 92%). MS: 451.2. 1H NMR (d4-MeOH): 7.88-7.83 (m, 1 H), 7.62-7.51 (m, 3H), 7.50-7.44 (m, 2H), 7.42-7.36 (m, 2H), 7.34-7.24 (m, 3H), 7.22-7.17 (m, 1 H), 3.71-3.60 (m, 6H), 2.61-2.55 (m, 4H), 2.53 (s, 3H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With pyrrolidine In water at 100℃; for 5h; | |
79% | With C22H20Cl4N4O2PdS; potassium carbonate In ethanol at 80℃; for 1h; | General procedure for the catalytic Sonogashira cross-coupling General procedure: K2CO3 (2.5 × 10-4 mol, 2.5 equiv), aryl iodide (1.0 × 10-4 mol, 1.0 equiv), and alkyne (1.5 × 10-4 mol, 1.5 equiv) were mixed in a 10-mL vial, followed by addition of a solution of the selected catalyst (1 × 10-8 mol) in EtOH (1 mL). The vial was placed in a preheated oil bath at 80 °C and stirred for 1 h. After cooling to 20-25 °C, the reaction mixture was evaporated to dryness under a stream of dinitrogen followed by addition of 1.0 equiv of 1,2-dimethoxyethane as NMR internal standard, and extraction of the reaction mixture with three 0.20-mL portions of CDCl3. All fractions were joined and analyzed by 1H NMR spectroscopy. The product peak assignments were based on the authentic samples or on published dat, whereas quantifications were performed upon integration of the selected peak of the product relatively to the peak of the standard. |
With C23H20Cl4N4OPd; potassium carbonate In ethanol at 80℃; for 4h; | General procedure for the catalytic Sonogashira cross-coupling General procedure: Selected base (1.5×10-4 mol, 1.5 equivs), aryl iodide (1.0×10-4 mol, 1.0 equiv) and terminal alkyne (1.0×10-4 mol, 1.0 equivs) were mixed in a 10-mL vial, followed by addition of a solution of the selected catalyst (1×10-8 mol) in EtOH (1 mL). The vial was placed in a pre heated oil bath at 80 °C and stirred for 4 h. After cooling to ca. 25 °C, the reaction mixture was evaporated to dryness under a stream of dinitrogen followed by addition of 1.0 equivof 1,2-dimethoxyethane (NMR internal standard), and extraction of the reaction mixture with three 0.20 mL portions of CDCl3. All fractions were joined and analyzed by 1H NMR spectroscopy. The product peak assignments were based on authentic samplesor on published data [56,62-68] (several sources were used for published compounds), while the structure of two new products,i.e. 3,4-dimethoxy-5-(phenylethynyl)benzaldehyde (derived from the coupling of 3-iodo-4,5-dimethoxybenzaldehyde with phenylacetylene) and 1-fluoro-2-[(2-methylphenyl)ethynyl]benzene (prepared from 2-fluorophenylacetylene and 2-iodotoluene were undoubtedly established using NMR spectroscopy, MS and elemental analyses (see Supplementary data). Quantifications were performed upon integration of the selected peak of the product in the 1H NMR relatively to the peak of the standard. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With tetrahydropyrrole In lithium hydroxide monohydrate at 100℃; for 44h; | |
78% | With potassium carbonate In methanol at 80℃; for 6h; Inert atmosphere; Green chemistry; | General experimental procedures for Sonogashira reaction General procedure: Stirring the mixture of aryl halide (1.00 mmol), phenylacetylene derivative (1.50 mmol), Pd(at)MOF-808 (3 mol %), K2CO3 (2.00 mmol) and methanol (5.00 mL) at 80 °C for 2-8 h. After cooling down the mixture to room temperature, evaporating the solution under reduced pressure. After that, purifying the residue by silica gel column chromatography to collect the target coupling products. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96% | With cobalt(III)((CH2NCHC6H4(O))2)(OAc); sulfuric acid In methanol; lithium hydroxide monohydrate at 80℃; for 20h; Schlenk technique; | |
94% | With ferric(III) chloride; lithium hydroxide monohydrate; silver(I) bis(trifluoromethanesulfonyl)imide In 1,4-dioxane at 80℃; for 40h; regioselective reaction; | |
94% | With sulfuric acid; C18H15CoN2O10S2(2-)*2Na(1+); lithium hydroxide monohydrate In methanol at 80℃; for 20h; Schlenk technique; | 2.2. General procedure for hydration of terminal alkynes General procedure: The 10 mL schlenk tube was charged with phenylacetylene (0.5 mmol, 51 mg), methanol (0.625 mL), catalyst (10 μmol, 2.0%), and then H2SO4 (10 μmol, 2.0%) dissolved in H2O (2.2mmol, 0.04 mL). The mixture was heated to 80 °C and at it for 20 h in a closed tube with a magnetic stirring bar. The progres sof the reaction was monitored using TLC and GC-MS. After the reaction, the mixture was cooled to room temperature, and CH2Cl2 (5 mL) and water (5 mL) were added to the mixture.The aqueous and organic layers were separated, and the aqueous phase was extracted with CH2Cl2 (5 mL 3). The combined organic extracts were washed with a saturated NaCl solution,dried over Na2SO4, and concentrated under reduced pressure. Then the product acetophenone was obtained. |
93% | With Au nanoparticles covalently bonded to HS/SO3H functionalized periodic mesoporous organosilica (Et) In lithium hydroxide monohydrate at 80℃; for 3h; | |
92% | With 4-methyl-morpholine; iodine In dimethyl sulfoxide at 120℃; for 16h; | Synthesis of acetophenone derivatives (2a-q) General procedure: A 10 mL reaction flask was charged with terminal alkynes 1a-q (1.0 mmol), I2 (0.3 mmol) and N-methyl morpholine (1.0 mmol) in DMSO (2.0 mL) and then the reaction mixture was heated at 120 °C for 16 h. After completion of the reaction (progress was monitored by TLC; SiO2, hexane/EtOAc = 9:1), the recation mixture was quenched with saturated sodium thiosulphate solution, diluted with water (20 mL) and extracted with ethyl acetate (3 × 15 mL). The combined organic layer was dried over anhydrous Na2SO4. Solvent was removed under reduced pressure and the remaining residue was purified over silica gel column chromatography using hexane/EtOAc = 4:1 as an eluent to obtain the desired products 2a-q in high yields. |
91% | With potassium tetrachloridoaurate(III); (S)-2-(2-(1H-benzo[d][1,2,3]triazol-1-yl)acetamido)propanoic acid; lithium hydroxide monohydrate; trifluoromethane sulfonic acid silver salt; glacial acetic acid Schlenk technique; Inert atmosphere; | |
91% | With C22H20AuN3O2P(1+)*CF3O3S(1-); lithium hydroxide monohydrate; trifluoromethane sulfonic acid silver salt; glacial acetic acid at 100℃; for 10h; | |
90% | With C20H14AuN2O2(1+)*Cl(1-); lithium hydroxide monohydrate; trifluoroacetic acid In methanol at 80℃; for 5h; Sealed tube; | 2.3 Typical procedure for the hydration of alkynes General procedure: Alkyne (0.5 mmol), catalyst (2.0 mol%), H2O (4.0 equiv., 0.04 mL) and CF3COOH (2.0 mol%) were dissolvedin MeOH (0.4 mL) and the homogeneous solution was stirred in a sealed tube at 80°C for 5 h. After the completion of the reaction, the mixture was cooled to room temperature, and then CH2Cl2 and H2O were added to it. The organic layer was separated and washed with brine, dried over Na2SO4, and concentrated under reduced pressure. The residue was purified over silica gel by column chromatography (25% EtOAc in hexane). |
90% | With morpholine; Au-TiO2; lithium hydroxide monohydrate In 1,4-dioxane at 120℃; for 1h; Microwave irradiation; | |
90% | With 3,4,5-trihydroxybenzoic acid; lithium hydroxide monohydrate at 60℃; for 6h; Sealed tube; Green chemistry; | |
90% | With trifluoromethane sulfonic acid silver salt In lithium hydroxide monohydrate; glacial acetic acid at 110℃; for 6h; Schlenk technique; | 2.6 Hydration of alkynes General procedure: To a 25mL Schlenk tube, AuSBA-15 (6wt%, 20mg), AgOTf (0.05mmol) was added to a solution of phenylacetylene (1.0mmol) in HOAc/H2O (3.0mL, 15:1) under ambient air, the resulting mixture was stirred for 6hat 110°C. It was monitored by TLC. After the reaction was completed, the solvent was removed under reduced pressure and purified of the crude product by column chromatography on silica-gel afforded the desired compound. |
88% | With lithium hydroxide monohydrate In Cyclooctan at 100℃; for 0.5h; | |
88% | With trifluorormethanesulfonic acid; AuCl*C33H53OP; C33H53OP*AuCl; lithium hydroxide monohydrate; trifluoromethane sulfonic acid silver salt In methanol at 20℃; for 19h; | |
84% | With lithium hydroxide monohydrate In methanol at 150℃; for 14h; Autoclave; Inert atmosphere; Green chemistry; | The general procedure of the reaction General procedure: In a 100 mL capacity of autoclave vessel a 60 mL solution of methanol and water (1:2) was added, further 1 mmol alkynes were added to this solution. The autoclave was three times purged withthe gas and then nally pressurized up to the 11 bar pressure. The reaction mixture was vigorously stirred at 150 °C for continuous 14 h. After the completion of the reaction, the reactor was cooled to room temperature, and then the argon pressure was carefully released to the atmospheric pressure. Methanol from the reaction mixture is removed using rotatory evaporator. After that, the reaction mixture was transferred in a separating funnel, and it wasworked up with ethyl acetate. The organic layer was separatedand dried over Na2SO4. Afterwards, it was filtered and concentrated under reduced pressure. The resulted crude mixture waspuried by silica gel column chromatography using ethyl acetate/n-hexane as eluent, and pure keto product was isolated. |
83% | With methanol In lithium hydroxide monohydrate at -5℃; for 0.5h; Irradiation; Green chemistry; | 2. Experimental General procedure: To a 100 mL capacity borosilicate immersion well of UV reactor, 80 mL aqueous methanol MeOH:H2O (1:2), alkyne (1 mmol), Rh catalyst (1.5 mol%) was added, and the reaction mixture was cooled to-5 °C. It was irradiated using a Hg vapor UV lamp, 125 W, 289 nm for30 min with continuous stirring. After completion of the reaction, the reaction mixture was left to warm to room temperature and then concentrated in vacuo. The residue was extracted with dichloromethaneand water, the organic phase was collected, dried with anhydrous Na2SO4, concentrated at reduced pressure, and puried by flash columnchromatography using hexane/ethyl acetate as eluent to obtain the corresponding product.The catalyst was synthesized as per the procedure reported in reference 15. |
82% | With lithium hydroxide monohydrate for 8h; Reflux; | General procedure for the hydration of alkyne 3 catalyzed by S-COPNA (NP) resin General procedure: The mixture of 3 (232 mg, 2.0 mmol) and S-COPNA (NP) resin (59 mg, 0.2 mmol) in H2O (4 mL) was stirred (600 rpm) for 8 h under reflux conditions (bath temp. 120 °C). The catalyst was filtered and washed with H2O and heptane. One drop of saturated NaHCO3 was added and the organic layer was evaporated under reduced pressure. The residue was purified by column chromatography with heptane-acetone (20:1) as eluent to afford 23 (225 mg, 84%). |
82% | With hydrogenchloride; lithium hydroxide monohydrate; copper chloride (I) In methanol at 20℃; for 6h; Irradiation; Inert atmosphere; | Preparation of phenylacetylene General procedure: A 10 mL reaction vessel with a magnetic stirring bar was equipped with phenylacetylene (1 mmol), CuCl (1 mol%), HCl (0.2 mL, 37 wt %) and methanol (2 mL). The mixture was irradiated with a blue LED (5 W) and stirred under at r.t. in an air atmosphere for 6 h. The distance of the reaction vial from the light is about 2 centimeter. After the reaction, the solvent was removed under reduced pressure. Purification of the crude product was achieved by flash column chromatography using petrol ether/ethyl acetate (6:1~10:1) as eluent. |
78% | With hydrogen tetrafluoroborate In chloroform-d1; lithium hydroxide monohydrate at 60℃; for 1h; | |
75% | With Au-SH(at)HSO3-SBA-15 In lithium hydroxide monohydrate at 80℃; for 4h; | |
29% | With hydrogenchloride; tetrakis-(triphenylphosphine)-palladium In tetrahydrofuran; lithium hydroxide monohydrate at 45℃; for 168h; Inert atmosphere; Schlenk technique; chemoselective reaction; | |
With hydrogenchloride; lithium hydroxide monohydrate; N-hexadecyl-N,N,N-trimethylammonium bromide In isopropanol at 140℃; for 7h; | ||
99 %Spectr. | With gallium trifluoromethanesulfonate; lithium hydroxide monohydrate; glacial acetic acid at 100℃; for 2h; | |
98 %Chromat. | With methanol; lithium hydroxide monohydrate; gold(I) chloride at 65℃; for 3h; Green chemistry; | General Procedure for Alkyne Hydration General procedure: In a 4 mL reaction vial equipped with a magnetic stirring bar,AuCl (5.8 mg, 0.025 mmol, 5 mol%) was added to MeOH (1 mL)under argon atmosphere. The reaction mixture was stirred for 5min, and then starting material (0.5 mmol, 1.0 equiv) and internalstandard dodecane (1.0 equiv) were added, followed bydefined amount of distilled H2O (4.0 equiv). The resulting reactionmixture was heated for 3 h, or for 24 h when needed, at65 °C. After completion of the reaction, the reaction mixturewas diluted and filtered using CH2Cl2 and injected in GC foranalysis. |
97 %Spectr. | With In(3+)*C48H24N4O8(6-)*Co(3+)*H2O; lithium hydroxide monohydrate In methanol at 80℃; for 72h; Sealed tube; | |
With tetrahydrothiophene gold(I) chloride; C42H38O4P2S In methanol; lithium hydroxide monohydrate at 120℃; for 3h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
99% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In tetrahydrofuran at 50℃; for 2h; Inert atmosphere; | |
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 50℃; for 4h; Inert atmosphere; | ||
Stage #1: 1-ethynyl-2-methylbenzene; ortho-bromobenzaldehyde With bis-triphenylphosphine-palladium(II) chloride; triethylamine for 0.0833333h; Stage #2: With copper(l) iodide at 50℃; for 4h; Inert atmosphere; |
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 50℃; for 4h; Inert atmosphere; | ||
With copper(l) iodide; triethylamine at 50℃; Inert atmosphere; | ||
With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 50℃; for 12h; Inert atmosphere; | ||
With copper(l) iodide; dichlorobis(tri-O-tolylphosphine)palladium In triethylamine at 50℃; for 12h; Inert atmosphere; | 4.2. Typical procedure for preparation of N-(o-arylethynyl)benzylp-toluenesuldonamide 1 General procedure: To a solution of o-bromobenzaldehyde (10.0 mmol, 1.85 g),PdCl2(PPh3)2 (0.2 mmol, 140.4 mg) and CuI (0.1 mmol, 19.0 mg) inEt3N (0.3 M) was added ethynylbenzene (12.0 mmol, 1.32 mL). Theobtained mixture was stirred for 12 h at 50C under argon atmosphere.Sat. aq. NH4Cl solution (15.0 mL) was added to the mixture, and the product was extracted with CHCl3 (15.0 mL 3). Theorganic layer was dried over Na2SO4 and filtered. After removal ofthe solvent under reduced pressure, the residue was purified bysilica-gel column chromatography (eluent: n-hexane:EtOAc 19:1)to give o-(phenylethynyl)benzaldehyde (1.96 g, 95%). To a solutionof o-(phenylethynyl)benzaldehyde in EtOH (1.0 M) was added hydroxylaminehydrochloride (1.2 equiv.). The mixture was stirred for1 h at room temperature. To the obtained mixture were slowlyadded Zn powder (2.5 equiv.) and hydrochloric acid (12.0 M, 4.0equiv.) at 0 C. The obtained mixture was stirred for 0.5 h at roomtemperature under argon atmosphere. A solution of ammonia(28e30%) was slowly added until pH S 7, and the product wasextracted with CHCl3 (15.0 mL 3). The organic layer was driedover Na2SO4 and filtered. After removal of the solvent underreduced pressure, p-toluenesulfonyl chloride (1.1 equiv.) and pyridine(0.5 M) were added to the residue in dichloromethane (1.0 M)at 0 C. The obtained mixture was stirred for 12 h at room temperatureunder argon atmosphere. Aq. NH4Cl solution (15.0 mL)was added to the mixture, and the product was extracted withCHCl3 (15.0 mL 3). Then, the organic layer was dried over Na2SO4and filtered. After removal of the solvent under reduced pressure,the residue was purified by silica-gel column chromatography(eluent: n-hexane:EtOAc 3:1) to give N-(o-phenylethynyl)benzylp-toluenesulfonamide 1A (2.76 g, 76%). Other N-(o-arylethynyl)benzyl p-toluenesulfonamides 1Be1W were obtained in 55%e78%yields by the same procedure. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With dichloro bis(acetonitrile) palladium(II); copper(l) iodide; diisopropylamine; XPhos In 1,4-dioxane at 80℃; for 10h; Inert atmosphere; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With [Cu(phen)(xantphosTEPD)]PF6; potassium carbonate In water; acetonitrile at 20℃; for 7h; Sealed tube; Inert atmosphere; Irradiation; diastereoselective reaction; | |
85% | With copper(I) oxide supported on ceria nanoparticle In ethanol at 90℃; for 1h; Inert atmosphere; Schlenk technique; | Substrate scope investigations with the Cu1-O(I)/CeO2 catalyst General procedure: In a typical procedure, B2Pin2 (0.7 mmol, 177.4 mg) and Cu1-O(I)/CeO2 (Cu = 0.5 mol %, 7.6 mg) were placed in adried Schlenk tube equipped with a stir bar. After evacuation under vacuum and flushing with N2 for three times,alkyne substrate (0.5 mmol) and ethanol (2.0 mL) were injected under the atmosphere of N2. The mixture wasultrasonically vibrated to form a uniform suspension and then stirred at 90oC for 1.0 h. Upon completion, the reactionmixture was analyzed by GC-MS to determine the selectivity of vinylboronate products. To determine the isolatedyield of the target product, the reaction mixture was centrifuged to remove the catalyst, and the supernate wasconcentrated in vacuum. The residue was purified by flash column chromatography on silica gel with petroleumether/ethyl acetate as eluent. |
75% | Stage #1: bis(pinacol)diborane With [1,3-bis(1-adamantyl)imidazolidin-2-yl]chloro-copper; sodium t-butanolate In tetrahydrofuran at 22℃; for 0.5h; Inert atmosphere; Stage #2: 1-ethynyl-2-methylbenzene With methanol In tetrahydrofuran at 22℃; for 12h; Inert atmosphere; regioselective reaction; |
73% | With tetrabutylammonium tetrafluoroborate In methanol at 20℃; Electrochemical reaction; | |
73% | With tetrabutylammonium tetrafluoroborate In methanol | |
70% | With [bis(acetoxy)iodo]benzene; sodium t-butanolate In ethanol at 20℃; for 12h; regioselective reaction; | |
Stage #1: bis(pinacol)diborane With copper; sodium methylate In 1,4-dioxane; ethanol for 0.5h; Inert atmosphere; Sealed tube; Stage #2: 1-ethynyl-2-methylbenzene In 1,4-dioxane; ethanol at 60℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: 1-ethynyl-2-methylbenzene; methyl 3-tert-butyldimethylsilyloxy-2-diazobut-3-enoate With Rh2(S-PTAD)4 In dichloromethane at 0℃; for 2.5h; Inert atmosphere; Stage #2: With tetrabutyl ammonium fluoride In dichloromethane at 23℃; Inert atmosphere; optical yield given as %ee; enantioselective reaction; | 4.3. General procedure for Rh(II)-catalyzed decompositions of siloxyvinyldiazoacetate 5 in the presence of acetylenes General procedure: A mixture of alkyne 6 (0.5 mmol) and Rh2(S-PTAD)4 (0.01 mmol) was dissolved in 1 mL of dichloromethane and stirred at -45 °C under an atmosphere of argon. Siloxyvinyldiazoacetate 5 (1.0 mmol) in 10 mL dichloromethane was then added to the reaction mixture via syringe pump over 2 h. After the complete addition, the reaction mixture was stirred for additional 20 min followed by addition of TBAF (1.0 mmol) in one portion. The reaction mixture was further stirred at 23 °C followed by aqueous work-up. The organic layer was dried over MgSO4, filtered, and concentrated. The residue was purified on silica using 10:1 hexane/diethyl ether followed by 1:1 hexane/EtOAc as eluents to afford the desired cyclopropenyl ketones. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With copper(l) iodide; trifuran-2-yl-phosphane; diisopropylamine; palladium dichloride In toluene at 55℃; Inert atmosphere; chemoselective reaction; | General procedure for chemoselective Sonogashira cross-coupling reaction of benzyl 5-bromo-2-iodophenylcarbamate (3) and arylalkynes (4a-o). General procedure: To a degassed solution of benzyl 5-bromo-2-iodophenylcarbamate 3 (0.50 mmol) and an arylalkyne 4 (0.52 mmol) in dry toluene (10.0 mL) under N2 was added diisopropylamine (0.60 mmol), palladium(II) chloride (0.03 mol), tri-2-furylphosphine (0.60 mol) and copper(I) iodide (0.03 mol). This mixture was stirred at 55 C. After completion of the reaction (typically less than 1 h) as indicated by TLC analysis, toluene was removed in vacuo and the residue was dissolved in dichloromethane and adsorbed on silica gel. After flash chromatography (SiO2-gel, elution with EtOAc/hexane gradient) the solid residue was dissolved in chloroform and petroleum ether was added to precipitate. Finally, the solid was triturated and washed with a chloroform/petroleum ether mixture to afford the desired pure product 5a-o. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With dichlorobis(1,4-dimesityl-1H-1,2,3-triazol-5-ylidene)palladium(II); cesium acetate In N,N-dimethyl acetamide at 100℃; for 15h; | 4.3. General procedures for Sonogashira coupling General procedure: Under an atmosphere of air, a 5 mL vial containing a stirring bar was charged with 1a (0.005 mmol), CsOAc (192.0 mg, 1.0 mmol) and DMA (3 mL), and subsequently were added aryl halide (0.5 mmol) and terminal alkyne (1.0 mmol). The vial was heated at 100 °C with magnetically stirring for 15 h. The mixture was quenched with water, extracted with dichloromethane, dried (MgSO4) and filtered. GC/MS analysis of the organic layer showed the presence of the corresponding coupling product (diaryl alkyne or aryl alkyl alkyne). The solvent was removed under reduced pressure to give crude products. The product was isolated by PTLC or its yield was determined by GC by using biphenyl as an internal standard. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With copper(l) iodide; tetrakis(triphenylphosphine) palladium(0); triethylamine In tetrahydrofuran at 60℃; for 6.16667h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With tris-(dibenzylideneacetone)dipalladium(0); C42H63O3P In 1,4-dioxane at 90℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With iron(III) chloride; di-tert-butyl peroxide In 1,2-dichloro-ethane at 80℃; for 12h; Schlenk technique; | General Procedure for Synthesis of Quinolines: General procedure: 1 (0.20 mmol), FeCl3 (0.02 mmol), 2 or 4 (0.24 mmol), and (tBuO)2 (0.40 mmol) were successively added to DCE (1 mL) in a Schlenk reaction tube. The mixture was stirred for 12 hours at 80 ºC. And then filtered through a small pad of silica gel, and concentrated in vacuo. Flash chromatography on silica gel using ethyl acetate/petroleum ether (1:4) furnished the final product. |
80% | With iron(III) trifluoromethanesulfonate; acetic acid In toluene at 140℃; for 24h; | |
70% | With manganese(II) bromide; dipotassium peroxodisulfate In acetonitrile at 90℃; for 24h; regioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | Stage #1: 1-ethynyl-2-methylbenzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: 1,3,5-cycloheptatrienylium tetrafluoroborate In tetrahydrofuran; hexane at -78 - 20℃; for 12h; Inert atmosphere; | |
79% | With copper(I) thiophene-2-carboxylate; anhydrous sodium sulphite In tetrahydrofuran at 50℃; for 16h; Sealed tube; Inert atmosphere; | |
71% | Stage #1: 1-ethynyl-2-methylbenzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.666667h; Inert atmosphere; Stage #2: 1,3,5-cycloheptatrienylium tetrafluoroborate In tetrahydrofuran; hexane at 20℃; for 5h; Inert atmosphere; |
57% | Stage #1: 1-ethynyl-2-methylbenzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 0.666667h; Inert atmosphere; Stage #2: 1,3,5-cycloheptatrienylium tetrafluoroborate In tetrahydrofuran; hexane at -78 - 23℃; for 5h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | With silver hexafluoroantimonate; dichloro(pentamethylcyclopentadienyl)rhodium (III) dimer In acetic acid at 20℃; for 12h; Schlenk technique; Inert atmosphere; | GENERAL PROCEDURE: General procedure: To a dried Schlenk tube was equipped with a magnetic stirbar. [Cp*RhCl2]2 (0.005 mmol, 2.5 mol %, 3.1 mg), AgSbF6 (0.03 mmol, 15 mol %,10.3 mg), substrate 1 (0.2 mmol or 0.4 mmol), HOAc (1 ml), substrate 2 (0.24 mmolor 0.2 mmol) were added sequentially under argon. The tube was stirred at roomtemperature or 80 °C for 12 h. After completion of the reaction, the mixture wasdiluted with EtOAc (10 mL), filtered through a short pad of silica gel and washedwith EtOAc (30 mL). The filtrate was pre-absorbed on silica gel and concentrated byrotary evaporation. The crude product was purified by flash silica gel (300-400 mesh)chromatography to afford the desired products product 3. |
80% | With bromopentacarbonylmanganese(I); N-cyclohexyl-cyclohexanamine In diethyl ether at 80℃; for 6h; Inert atmosphere; Schlenk technique; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With bromopentacarbonylmanganese(I); N-cyclohexyl-cyclohexanamine In diethyl ether at 80℃; for 6h; Inert atmosphere; Schlenk technique; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With bromopentacarbonylmanganese(I); N-cyclohexyl-cyclohexanamine In diethyl ether at 80℃; for 6h; Inert atmosphere; Schlenk technique; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With potassium hydroxide In dimethyl sulfoxide at 120℃; for 1.5h; Schlenk technique; Inert atmosphere; stereoselective reaction; | General procedure for the synthesis of substituted Z-styryl-1H-imidazole (3a-q) General procedure: To a solution of N-heterocycle (1a-f) (2.0 equiv) in DMSO and finely crushed KOH (20mol %), alkyne (2a-l) (1.0mmol) was added. Resulting mixture was heated at 120 °C for 1.5 h.Progress of the reaction was monitored by TLC and after the completeconsumption of alkynes; reaction mixture was brought to room temperature. After that reaction mixture was extracted with ethylacetate and water. The organic layer was washed with brine and dried over Na2SO4.The solvent was evaporated in vacuo and the crudes obtained werepurified by column chromatography (hexane and ethyl acetate) to afford thedesired product in good yields. |
With 1-methyl-pyrrolidin-2-one; cesiumhydroxide monohydrate at 120℃; for 24h; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With di(pyridin-2-yl)amine; dichlorodihydroxopalladium(II); triethylamine In lithium hydroxide monohydrate at 25℃; for 6h; Inert atmosphere; | |
90% | With C42H48Cl4N4Pd2S2; triethylamine In acetonitrile at 60℃; for 24h; Inert atmosphere; | |
90% | With potassium carbonate In methanol at 80℃; for 2h; Inert atmosphere; Green chemistry; | General experimental procedures for Sonogashira reaction General procedure: Stirring the mixture of aryl halide (1.00 mmol), phenylacetylene derivative (1.50 mmol), Pd(at)MOF-808 (3 mol %), K2CO3 (2.00 mmol) and methanol (5.00 mL) at 80 °C for 2-8 h. After cooling down the mixture to room temperature, evaporating the solution under reduced pressure. After that, purifying the residue by silica gel column chromatography to collect the target coupling products. |
85% | With [Cu(N,N'-di-methylethylenediamine)2]Cl2·H2O; Cs2CO3; N<SUB>1</SUB>,N<SUB>2</SUB>-dimethylethane-1,2-diamine In 1,4-dioxane; methanol at 135℃; for 22h; Inert atmosphere; | |
76% | With 1,4-diaza-bicyclo[2.2.2]octane; manganese(III) triacetate dihydrate at 70℃; Green chemistry; | General procedure: General procedure: In a 25 mL reaction tube, Mn(OAc)3.2H2O(10 mol%), DABCO (2.5 equiv.) and a stirring bar were added. Then iodobenzene(1 mmol), phenyl acetylene (1 mmol) and PEG-400 were injected by syringe. The reaction tube was closed and transferred to a 70 °C oil bath for 19-24 hours. After the reaction completed, cool down the reaction mixture to room temperature. Water (2 mL) was added and the reaction mixture was extracted with ethyl acetate and then concentrated and purified by column chromatography. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80 %Chromat. | With (p-cymene)ruthenium(II) chloride; ethene; 1,3-bis-(2,6-diisopropylphenyl)-imidazol-2-ylidene In toluene at 80℃; for 1h; | 2.2. Tandem enyne metathesis/Diels-Alder reactions of arylalkynes General procedure: A reactor was charged with [RuCl2(p-cymene)]2 (0.033 mmol), IPr, (0.066 mmol), and alkyne (0.66 mmol) in 3 ml of toluene and heated to 80 °C under an ethylene atmosphere (1 atm) for 1 h. After complete conversion to the 1,3-diene product was observed, dienophile (0.154 mmol) was added under a nitrogen atmosphere, and the reaction was stirred at 80 °C for 8 h. The reaction mixture was analyzed by GC-MS. The solvents were evaporated under reduced pressure, and the crude product mixture was purified by column chromatography, resulting product was analyzed by 1H and 13C NMR analysis. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With potassium carbonate In methanol at 80℃; for 2h; Inert atmosphere; Green chemistry; | General experimental procedures for Sonogashira reaction General procedure: Stirring the mixture of aryl halide (1.00 mmol), phenylacetylene derivative (1.50 mmol), Pd(at)MOF-808 (3 mol %), K2CO3 (2.00 mmol) and methanol (5.00 mL) at 80 °C for 2-8 h. After cooling down the mixture to room temperature, evaporating the solution under reduced pressure. After that, purifying the residue by silica gel column chromatography to collect the target coupling products. |
87% | With di(pyridin-2-yl)amine; dichlorodihydroxopalladium(II); triethylamine In lithium hydroxide monohydrate at 25℃; for 6h; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | Stage #1: 1-ethynyl-2-methylbenzene With n-butyllithium In tetrahydrofuran; hexane at -78℃; for 1h; Inert atmosphere; Stage #2: Trimethyl borate In tetrahydrofuran; hexane at -30 - 20℃; for 2h; Stage #3: With potassium hydrogenfluoride In tetrahydrofuran; hexane; water at -20 - 20℃; for 2h; | General procedure for preparation of potassium alkynyltrifluoroborates (Scheme 2) General procedure: n-BuLi (4.70mL, 1.6M in hexane, 7.57mmol, 1.0equiv) was added dropwise to a solution of acetylene (7.57mmol, 1.0equiv) in 7.6mL of dry THF at -78°C under a nitrogen atmosphere. After 60min at this temperature, trimethylborate (1.10g, 11.3mmol, 1.5equiv) was added dropwise at -30°C. The mixture was stirred at this temperature for 60min and slowly allowed to warm to room temperature within another 60min. A saturated 4.5M aqueous solution of potassium hydrogen difluoride (KHF2) (10.1mL, 45.3mmol, 6.0equiv) was added at -20°C to the vigorously stirred solution. The resulting mixture was continued to stir for 60min at -20°C after which it was allowed to warm to room temperature for 60min. The solvent was removed under reduced pressure, and the resulting white solid was dried under high vacuum to remove water. The solid was washed first with acetone and then with hot acetone. The solution was concentrated to afford a white solid. The solid was dissolved in minimum amount of hot acetone, precipitated by adding methyl tert-butyl ether (MTBE), after which the solution was cooled to -20°C to complete precipitation of the solid. The product was collected as an off white solid 2a-o in 40-80% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With ferric(III) chloride; potassium peroxodisulfate; oxygen In water monomer at 20℃; for 9h; Green chemistry; | General procedure for the one-pot synthesis of β-keto sulfones 3a-w General procedure: A mixture of alkyne 1 (0.25 mmol), sodium sulfinate 2 (0.375 mmol), FeCl3 (20 mol %),K2S2O8 (20 mol %), and water (3 mL) was stirred at rt in an open flask for 6-9 h(Table 2). After completion of the reaction (monitored by TLC), the mixture was extracted with EtOAc (3 5 mL). The combined organic phases were dried over anhyd. Na2SO4, filtered, and concentrated under reduced pressure. The resulting crude product was purified by silica gel column chromatography using a mixture of EtOAc-n-hexane (1:4) as eluent to afford an analytically pure sample of β-keto sulfones 3 (Table 2). |
79% | With oxygen at 20℃; for 4h; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 20℃; Inert atmosphere; | Synthesis of various Substrates 1 General procedure: To a solution of S2 (2.47 g, 10 mmol), CuI (76 mg, 0.4 mmol), Pd(PPh3)2Cl2 (140 mg, 0.2 mmol) under a nitrogen atmosphere was added anhydrous Et3N (20 mL) and terminal acetylene (12 mmol). The solution was stirred at room temperature for appropriate time. The reaction was monitored by TLC, then the crude product was purified by silica gel column chromatography (PE) to afford pure 1 as oil. |
82% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine at 20℃; Inert atmosphere; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
262 mg | With potassium hydroxide In dimethyl sulfoxide at 130℃; for 1h; | One-Pot Sonogashira-Glaser Cyclization/Synthesis of Thiophenes; General procedure: A mixture of a (hetero)aryl iodide 1 (2.00 mmol), Pd(PPh3)2Cl2(28.1 mg, 0.04 mmol, 2 mol%), and CuCl (7.92 mg, 0.08 mmol, 4mol%) was dissolved in DMSO (1.00 mL) in a 8 mL microwavevessel equipped with a stirring bar and a septum and was degassedwith N2 for 5 min. After the addition of TMSA (0.42 mL,3.00 mmol) and anhydrous Et3N (0.55 mL, 4.00 mmol), the solutionwas stirred at r.t. for 1 h. Then, KF (232 mg, 4.00 mmol) wasadded and the reaction mixture was vigorously stirred under air inthe open reaction vessel at r.t. for 16 h. After the addition of themethanethiol 2 (or 6, 8) (1.20 mmol, 0.6 equiv), KOH (224 mg,4 mmol), and DMSO (1.00 mL), the mixture was heated in the microwavecavity at 130°C for 1 h. After cooling to r.t., the solventswere removed under reduced pressure. The residue was absorbed onCelite and purified by column chromatography on silica gel with n-hexane or n-hexane-THF (100:1) as eluent. The experimental detailsare shown in Table 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
147 mg | With potassium hydroxide In dimethyl sulfoxide at 130℃; for 1h; | One-Pot Sonogashira-Glaser Cyclization/Synthesis of Thiophenes; General procedure: A mixture of a (hetero)aryl iodide 1 (2.00 mmol), Pd(PPh3)2Cl2(28.1 mg, 0.04 mmol, 2 mol%), and CuCl (7.92 mg, 0.08 mmol, 4mol%) was dissolved in DMSO (1.00 mL) in a 8 mL microwavevessel equipped with a stirring bar and a septum and was degassedwith N2 for 5 min. After the addition of TMSA (0.42 mL,3.00 mmol) and anhydrous Et3N (0.55 mL, 4.00 mmol), the solutionwas stirred at r.t. for 1 h. Then, KF (232 mg, 4.00 mmol) wasadded and the reaction mixture was vigorously stirred under air inthe open reaction vessel at r.t. for 16 h. After the addition of themethanethiol 2 (or 6, 8) (1.20 mmol, 0.6 equiv), KOH (224 mg,4 mmol), and DMSO (1.00 mL), the mixture was heated in the microwavecavity at 130°C for 1 h. After cooling to r.t., the solventswere removed under reduced pressure. The residue was absorbed onCelite and purified by column chromatography on silica gel with n-hexane or n-hexane-THF (100:1) as eluent. The experimental detailsare shown in Table 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With potassium carbonate; triphenylphosphine at 60℃; for 6h; | 2-Phenylbenzofuran (1a); Typical Procedure General procedure: A freshly prepared solution of PdNPs (12.5 mL) was taken up in a 25-mL round-bottomed flask. To this solution K2CO3 (0.276 g, 2 mmol)and Ph3P (0.052 g, 0.2 mmol) were added followed by 2-iodophenol(0.22 g, 1 mmol) and phenylacetylene (0.122 g, 1.2 mmol). Then, themixture was stirred at 60 °C under aerobic conditions. The reactionwas monitored by TLC until complete consumption of phenylacetylene.When the reaction was complete, the solvents were evaporatedand the residue was purified by column chromatography (hexane-EtOAc). Yields for all compounds are calculated after column chromatography.The catalyst could be recycled. The size of the PdNPs afterfour catalytic cycles was found in the range of 12-18 nm by TEM analysisindicating some agglomeration.The reactions of 2-iodophenol or methyl 4-hydroxy-3-iodobenzoatewith arylacetylenes were carried out as given in the typical procedure.However, reactions using alkylacetylenes did not require theuse of Ph3P. |
81% | With potassium phosphate In N,N-dimethyl-formamide at 160℃; Schlenk technique; Inert atmosphere; Glovebox; Green chemistry; | 2.3. Typical procedure for one-pot tandem reaction between o-iodophenolsand terminal alkynes General procedure: General produce: o-iodophenol (0.5 mmol), alkyne (1.0 mmol) andbase (1.0 mmol) were added into a 10 mL dry Schlenk tube under Ar,then anhydrous DMF (5 mL) was injected into the mixture using syringe.Then the solution stirred at preheated oil bath (160 °C). The reactionwas monitored by TLC and GC.The mixture was cooled down toroom temperature after full conversion, then diluted with dichloromethaneand washed with water three times. The organic layerwas separated and washed with brine followed by drying with anhydrousNa2SO4. The filtrate was concentrated in vacuo to afford thecrude product, which was purified by flash column chromatography onsilica gel (petroleum ether). |
78% | With copper(l) iodide; <i>L</i>-proline; sodium hydroxide In dimethyl sulfoxide at 80℃; for 12h; Inert atmosphere; Sealed tube; | General Procedure for the Synthesis of 2-substituted benzo[b]furan/furo-pyridines 3 General procedure: A sealable reaction tube equipped with a magnetic stirrer bar was charged with 2-iodophenols 1 (1 mmol), alkynes 2 (1 mmol), NaOH (2 mmol), CuI (0.1 mmol), proline (0.3 mmol) and DMSO (5 mL), and the reaction vessel placed in an oil bath at 80 °C under N2 . After stirring the mixture at this temperature for 12 h, it was cooled to room temperature and diluted with ethyl acetate, washed with water and brine, dried over by MgSO4. After the solvent was removed under reduced pressure, the residue was purified by column chromatography on silica gel to afford the corresponding product. |
81 %Spectr. | With potassium phosphate In N,N-dimethyl-formamide at 160℃; for 5h; Sealed tube; Inert atmosphere; | 3 Preparation of 2- (o-methylphenyl) benzofuran: Weigh 10 mg of the above catalyst, 0.5 mmol of compound 1, and 1 mmol of K3PO4 solids into a 10 ml Shrek tube, seal the mouth of the tube with a rubber stopper, protect it with vacuum and argon, and use a micro sampler to pass 1 mmol of compound 2 and 5 ml of DMF Solvent was injected into the reaction system.The reaction tube was placed in an oil bath at 160 ° C, and the reaction was completed for 5 hours. The catalyst was filtered off to obtain a uniform reaction solution, washed with water to remove DMF, and then dried.Separation by column chromatography gave 2- (o-methylphenyl) benzofuran of the following structural formula II, with a nuclear magnetic yield of 81%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With C22H20Cl4N4O2PdS; potassium carbonate; In ethanol; at 80℃; for 1h; | General procedure: K2CO3 (2.5 × 10-4 mol, 2.5 equiv), aryl iodide (1.0 × 10-4 mol, 1.0 equiv), and alkyne (1.5 × 10-4 mol, 1.5 equiv) were mixed in a 10-mL vial, followed by addition of a solution of the selected catalyst (1 × 10-8 mol) in EtOH (1 mL). The vial was placed in a preheated oil bath at 80 C and stirred for 1 h. After cooling to 20-25 C, the reaction mixture was evaporated to dryness under a stream of dinitrogen followed by addition of 1.0 equiv of 1,2-dimethoxyethane as NMR internal standard, and extraction of the reaction mixture with three 0.20-mL portions of CDCl3. All fractions were joined and analyzed by 1H NMR spectroscopy. The product peak assignments were based on the authentic samples or on published dat, whereas quantifications were performed upon integration of the selected peak of the product relatively to the peak of the standard. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With (1,1'-bis(diphenylphosphino)ferrocene)palladium(II) dichloride; copper(l) iodide; triethylamine; In toluene; for 24h;Reflux; | General procedure: 2-(Methylthio)benzoxazoles or 2-(methylthio)benzothiazoles 1 (0.5 mmoles) were dissolved in 3 mL toluene. To the resulted solution were added the corresponding alkyne 2 (3 eq.), triethylamine (3 eq.), CuI (20 mol%) and Pd(dppf)Cl2 (10 mol%) and the mixture was stirred to reflux in air for 24 hours.The solvent was removed in vacuo and the residue was column cromatographed using various solvent mixtures to yield pure products 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With bis-triphenylphosphine-palladium(II) chloride; copper(l) iodide; triethylamine In acetonitrile at 70℃; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With copper(II) sulfate; sodium L-ascorbate In water; <i>tert</i>-butyl alcohol at 20℃; for 24h; | 3.4.3. Preparation of Tertiary 1,2,3-Triazoloamide 2 General procedure: To a mixture of α-azidoamide 16aa (34 mg, 0.20 mmol) and phenylacetylene (9a; 24 L,0.20 mmol) in t-BuOH/H2O (2 mL, 1:1) were added 0.5 M CuSO4 (0.020 mL, 0.010 mmol) and 1.0 M sodium ascorbate (0.020 mL, 0.020 mmol). The reaction mixture was stirred at room temperature for 1 day, and then the resulting reaction mixture was filtered. The separated solid was washed with H2O and hexanes, and triturated with hexane/EtOAc (10:1) to give the 1-morpholino-2-(4-phenyl-1H-1,2,3-triazol-1-yl)ethanone (2aaa; 52 mg, 96%) as a white solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With copper(II) sulfate; sodium L-ascorbate In water; <i>tert</i>-butyl alcohol at 20℃; for 24h; | 3.4.3. Preparation of Tertiary 1,2,3-Triazoloamide 2 General procedure: To a mixture of α-azidoamide 16aa (34 mg, 0.20 mmol) and phenylacetylene (9a; 24 L,0.20 mmol) in t-BuOH/H2O (2 mL, 1:1) were added 0.5 M CuSO4 (0.020 mL, 0.010 mmol) and 1.0 M sodium ascorbate (0.020 mL, 0.020 mmol). The reaction mixture was stirred at room temperature for 1 day, and then the resulting reaction mixture was filtered. The separated solid was washed with H2O and hexanes, and triturated with hexane/EtOAc (10:1) to give the 1-morpholino-2-(4-phenyl-1H-1,2,3-triazol-1-yl)ethanone (2aaa; 52 mg, 96%) as a white solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With copper(II) sulfate; sodium L-ascorbate In water; <i>tert</i>-butyl alcohol at 20℃; for 24h; | 3.4.3. Preparation of Tertiary 1,2,3-Triazoloamide 2 General procedure: To a mixture of α-azidoamide 16aa (34 mg, 0.20 mmol) and phenylacetylene (9a; 24 L,0.20 mmol) in t-BuOH/H2O (2 mL, 1:1) were added 0.5 M CuSO4 (0.020 mL, 0.010 mmol) and 1.0 M sodium ascorbate (0.020 mL, 0.020 mmol). The reaction mixture was stirred at room temperature for 1 day, and then the resulting reaction mixture was filtered. The separated solid was washed with H2O and hexanes, and triturated with hexane/EtOAc (10:1) to give the 1-morpholino-2-(4-phenyl-1H-1,2,3-triazol-1-yl)ethanone (2aaa; 52 mg, 96%) as a white solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With copper(II) sulfate; sodium L-ascorbate In water; <i>tert</i>-butyl alcohol at 20℃; for 24h; | 3.4.3. Preparation of Tertiary 1,2,3-Triazoloamide 2 General procedure: To a mixture of α-azidoamide 16aa (34 mg, 0.20 mmol) and phenylacetylene (9a; 24 L,0.20 mmol) in t-BuOH/H2O (2 mL, 1:1) were added 0.5 M CuSO4 (0.020 mL, 0.010 mmol) and 1.0 M sodium ascorbate (0.020 mL, 0.020 mmol). The reaction mixture was stirred at room temperature for 1 day, and then the resulting reaction mixture was filtered. The separated solid was washed with H2O and hexanes, and triturated with hexane/EtOAc (10:1) to give the 1-morpholino-2-(4-phenyl-1H-1,2,3-triazol-1-yl)ethanone (2aaa; 52 mg, 96%) as a white solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
98% | With copper(II) sulfate; sodium L-ascorbate In water; <i>tert</i>-butyl alcohol at 20℃; for 24h; | 3.4.3. Preparation of Tertiary 1,2,3-Triazoloamide 2 General procedure: To a mixture of α-azidoamide 16aa (34 mg, 0.20 mmol) and phenylacetylene (9a; 24 L,0.20 mmol) in t-BuOH/H2O (2 mL, 1:1) were added 0.5 M CuSO4 (0.020 mL, 0.010 mmol) and 1.0 M sodium ascorbate (0.020 mL, 0.020 mmol). The reaction mixture was stirred at room temperature for 1 day, and then the resulting reaction mixture was filtered. The separated solid was washed with H2O and hexanes, and triturated with hexane/EtOAc (10:1) to give the 1-morpholino-2-(4-phenyl-1H-1,2,3-triazol-1-yl)ethanone (2aaa; 52 mg, 96%) as a white solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With copper(II) sulfate; sodium L-ascorbate In water; <i>tert</i>-butyl alcohol at 20℃; for 24h; | 3.4.3. Preparation of Tertiary 1,2,3-Triazoloamide 2 General procedure: To a mixture of α-azidoamide 16aa (34 mg, 0.20 mmol) and phenylacetylene (9a; 24 L,0.20 mmol) in t-BuOH/H2O (2 mL, 1:1) were added 0.5 M CuSO4 (0.020 mL, 0.010 mmol) and 1.0 M sodium ascorbate (0.020 mL, 0.020 mmol). The reaction mixture was stirred at room temperature for 1 day, and then the resulting reaction mixture was filtered. The separated solid was washed with H2O and hexanes, and triturated with hexane/EtOAc (10:1) to give the 1-morpholino-2-(4-phenyl-1H-1,2,3-triazol-1-yl)ethanone (2aaa; 52 mg, 96%) as a white solid |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
82% | With copper(l) iodide; bis(acetonitrile)palladium(II) chloride; diisopropylamine; XPhos In 1,4-dioxane at 100℃; for 20h; Sealed tube; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With oxygen; rhodamine B In isopropyl alcohol at 20℃; for 12h; Irradiation; regioselective reaction; | |
74% | With water; oxygen; lithium hydroxide In N,N-dimethyl-formamide at 60℃; for 3h; | β-Keto Phosphonate Derivatives 3a-w; General Procedure General procedure: alkyne 1 (0.25 mmol), H-phosphonate 2 (0.5 mmol), LiOH (0.05mmol), DMF (2 mL), and H2O (0.25 mL), and the mixture wasstirred at 60 °C for 3 h under O2 (balloon). When the reactionwas complete, it was quenched with aq NaHCO3 (20 mL) and themixture was extracted with EtOAc (3 × 10 mL). The combinedorganic layers were washed with sat. brine (×2) then dried(MgSO4), filtered, and concentrated in vacuum. The crudeproduct was purified by chromatography [silica gel, CH2Cl2-MeOH (30:1 to 50:1)]. |
65% | With oxygen; copper(l) cyanide In dimethyl sulfoxide at 55℃; for 24h; | General procedure for construction of β-ketophosphine oxides General procedure: An oven-dried flask with the mixture of CuCN (0.025 mmol), alkynes 1 (0.5 mmol), H-phosphine oxides 2 (1.0 mmol) and DMSO (1.0 ml) was charged with O2. The reaction mixture was stirred at 55 °C for 24 hours. After completion of the reaction, water (10 ml) was added and extracted with EtOAc (5.0 ml×3). The combined organic layers were dried over anhydrous Na2SO4 and the solvent was removed under reduced pressure. The resulting mixture purified by flash column chromatography using a mixture of petroleum ether and ethyl acetate as eluent to give the desired products 3 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
51% | With hydrogen tetrachloroaurate(III) tetrahydrate In 1,1,2,2-tetrachloroethane at 50℃; for 15h; Inert atmosphere; Schlenk technique; Sealed tube; | General procedure for the nucleophilic addition reaction General procedure: A flame-dried Schlenk tube was charged with N-benzyl-α,β-unsaturated-γ-lactam 1 (0.5 mmol). The tube was then transferred to a glove box, where it was charged with Brönsted acid (0.05 mmol). The tube was removed from the glove box and attached to a Schlenk line, where it was charged with terminal alkyne 2 (1.5 mmol) and solvent (2.0 mL) via a syringe under a N2 atmosphere. The tube was then sealed and the reaction mixture was stirred at 50 °C for 15 h. The reaction was cooled to room temperature and evaporated to dryness under vacuum to give a residue, which was purified by flash column chromatography over silica gel (EA:PE = 1:100 to 1:3, v/v) to afford the desired product 3.; 1-Benzyl-5-(2-tolylethynyl)pyrrolidin-2-one (3b). This compound was prepared using the general procedure described above and purified by flash column chromatography to give a colorless oil, 73 mg, 51% yield. 1H NMR (400 MHz, CDCl3): δ 2.17-2.25 (m, 1H), 2.33-2.40 (m, 1H), 2.42 (s, 3H), 2.45-2.51 (m, 1H), 2.60-2.68 (m, 1H), 4.14 (d, J = 14.4 Hz, 1H), 4.40 (dd, J1 = 5.2 Hz, J2 = 8.0 Hz, 1H), 5.17 (d, J = 14.4 Hz, 1H), 7.13-7.39 (m, 9H); 13C NMR (100 MHz, CDCl3): δ 20.8, 26.4, 30.1, 44.7, 49.2, 84.5, 90.3, 122.0, 125.7, 127.7, 128.6, 128.7, 129.5, 132.1, 136.2, 140.2, 174.1; HRMS (ESI): m/z 290.1545 for [M+H]+, Calcd. for C20H20NO = 290.1539. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
93% | With boron trifluoride diethyl etherate; 2,3-dicyano-5,6-dichloro-p-benzoquinone In chloroform; toluene at 80℃; for 2h; | 2 Synthesis of 7-bromo-2- (2-methylphenyl) naphtho [2,1-b] furan 0.24 mmol of 2,3-dichloro-5,6-dicyano-p-benzoquinone, 0.20 mmol of 6-bromo-2-naphthol, 0.80 mmol of o-methylphenylacetylene,1.6ml of mixed solvent toluene and 0.4ml of chloroform,Boron trifluoride diethyl ether solution 0.01 mmol.Heated to 80 ,Continue stirring 2h,Stop the reaction,Cool to room temperature,Washed with saturated sodium chloride solution,Extraction with dichloromethane,dry,The solvent was distilled off under reduced pressure,The crude product was separated by column chromatography to obtain the desired product,Yield 93%. |
92% | With boron trifluoride diethyl etherate; 2,3-dicyano-5,6-dichloro-p-benzoquinone In chloroform; toluene at 80℃; for 2h; Inert atmosphere; Schlenk technique; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium (II) In 1,4-dioxane at 90℃; for 0.166667h; Microwave irradiation; | 83 Example 83: 1-(2,3-dimethylphenyl)-4-(3-(5-(o-tolyl)-1H-1,2,3-triazol-1-yl)propyl)piperazine(Compound 83) 1-(3-azidopropyl)-4-(2,3 dimethylphenyl)piperazine (50 mg, 0.23 mmol) and 1-ethynyl-2-methylbenzene (34 mg, 0.3 mmol), and chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II) catalyst (4.8 mg, 3 mol%) weremelted in the reaction container in 1,4-dioxane and it heated and reacted for 10 minutes at the microwave reactor to 90 temperature. The reaction progress and termination confirmed with TLC. The reaction mixture the intended compound of 61 mg (85%) was obtained after the reaction completion using column chromatographies (EtOAC : IPA = 9:1,v/v). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With copper nanoparticles on activated carbon In 1,4-dioxane at 60℃; for 0.166667h; Microwave irradiation; | 27 Example 27: 1-(3,4-dimethylphenyl)-4-(3-(4-(o-tolyl)-1H-1,2,3-triazol-1-yl)propyl)piperazine(Compound 27) 1-(3-azidopropyl)-4-(3,4-dimethylphenyl)piperazine (50 mg, 0.23 mmol) and 1-ethynyl-2-methyl benzene (33 mg, 0.31 mmol), and copper /catalyst of activated carbon (100 mg, 2 mol%) were melted in the reaction container in 1,4-dioxane and it heated and reacted for 10 minutes at themicrowave reactor to 60 temperature. The reaction progress and termination confirmed with TLC. The reaction mixture the intended compound of 68mg (91%) was obtained after the reaction completion using column chromatographies (EtOAC : IPA =9:1, v/v). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
85% | With chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium (II) In 1,4-dioxane at 90℃; for 0.166667h; Microwave irradiation; | 104 Example 104; 1-(2-fluorophenyl)-4-(3-(5-(o-tolyl)-1H-1,2,3-triazol-1-yl)propyl)piperazine(Compound 104) 1-(3-azidopropyl)-4-(2-fluorophenyl)piperazine(50 mg, 0.23 mmol) and 1-ethynyl-2-methylbenzene (38 mg, 0.32 mmol), and chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II)catalyst (4.8 mg, 3 mol%) were melted in the reaction container in 1,4dioxaneand it heated and reacted for 10 minutes at the microwave reactor to 90 temperature. The reaction progress and termination confirmed with TLC. The reaction mixture the intended compound of 63 mg (85%) was obtained after the reaction completion using column chromatographies (EtOAC : IPA = 9:1,v/v). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
92% | With chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium (II) In 1,4-dioxane at 90℃; for 0.166667h; Microwave irradiation; | 118 Example 118: 1-(2,3-dimethylphenyl)-4-(3-(5-(o-tolyl)-1H-1,2,3-triazol-1-yl)butyl)piperazine(Compound 118) 1-(3-azidobutyl)-4-(2,3-dimethylphenyl)piperazine(50 mg, 0.19 mmol) and 1-ethynyl-2-methylbenzene(30 mg, 0.29 mmol), and chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II) catalyst (4.8 mg, 3 mol%) were melted in the reaction container in 1,4-dioxane and it heated and reacted for 10 minutes at the microwave reactor to 90 temperature. The reactionprogress and termination confirmed with TLC. Thereaction mixture the intended compound of 66 mg(92%) was obtained after the reaction completionusing column chromatographies (EtOAC : IPA = 9:1, v/v). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
89% | With chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium (II) In 1,4-dioxane at 90℃; for 0.166667h; Microwave irradiation; | 125 Example 125: 1-(2,3-dichlorophenyl)-4-(3-(5-(o-tolyl)-1H-1,2,3-triazol-1-yl)butyl)piperazine(Compound 125) 1-(3-azidobutyl)-4-(2,3-dichlorophenyl)piperazine(50 mg, 0.19 mmol) and 1-ethynyl-2-methylbenzene(30 mg, 0.29 mmol), and chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II) catalyst (4.8 mg, 3 mol%) weremelted in the reaction container in 1,4-dioxane and it heated and reacted for 10 minutes at the microwave reactor to 90 temperature. The reaction progress and termination confirmed with TLC. The reaction mixture the intended compound of 62 mg (89%) was obtained after the reaction completion using column chromatographies (EtOAC : IPA = 9:1,v/v). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With chloro(cyclopentadienyl)bis(triphenylphosphine)ruthenium (II) In 1,4-dioxane at 90℃; for 0.166667h; Microwave irradiation; | 139 Example 139: 1-(2-fluorophenyl)-4-(3-(5-(o-tolyl)-1H-1,2,3-triazol-1-yl)butyl)piperazine(Compound 139) 1-(3-azidobutyl)-4-(2-fluorophenyl)piperazine (50 mg, 0.19 mmol) and 1-ethynyl-2-methylbenzene (30 mg, 0.29 mmol), and chlorocyclopentadienylbis(triphenylphosphine)ruthenium(II) catalyst (4.8 mg, 3 mol%) were melted in the reaction container in 1,4-dioxaneand it heated and reacted for 10 minutes at the microwave reactor to 90 temperature. The reaction progress and termination confirmed with TLC. The reaction mixture the intended compound of 64 mg (90%) was obtained after the reaction completion using column chromatographies (EtOAC : IPA = 9:1,v/v). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90.5% | With copper(ll) sulfate pentahydrate; sodium L-ascorbate In tetrahydrofuran; water at 20℃; for 16h; | 4.1.8 General procedure for the synthesis of click compounds (41-90) General procedure: To a solution of Group I (41-66), Group II (20-21) or Group III (26-27) azides (0.1-0.18mmol) in anhydrous THF (1.5mL) were added alkynes 30-40 (0.11-0.2mmol) and solid copper sulfate pentahydrate (0.1-0.18mmol) at room temperature. To this mixture was then added a solution of sodium ascorbate (0.5-0.09mmol) in water (1mL). The resulting reaction mixture was stirred at room temperature (16h). The progress of reaction, as indicated by formation of the less-mobile product, was monitored by TLC. After completion of reaction as indicated by TLC, the THF was removed under vacuum and the residue was partitioned between dichloromethane (15mL) and water (10mL). The organic layer was separated, dried over anhydrous sodium sulfate and filtered. Concentration of the filtrate afforded the usually solid crude residues which was purified by column chromatography (hexanes/EtOAc, 7.5:2.5; or chloroform/methanol, 9:1). to give the corresponding pure triazoles 41-90 (See Supporting information). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86% | With copper(l) iodide; palladium on activated charcoal; triethylamine; triphenylphosphine; In ethanol; at 60℃; for 5h; | General procedure: To <strong>[49679-45-0]ethyl <strong>[49679-45-0]3-chloroquinoxaline-2-carboxylate</strong></strong> 1 (1 g, 4.22 mmol),appropriate acetylene derivative (3.33 mmol, 1.5 eq.) in ethanol(15 mL) was added in a two-necked flask containing triethylamine(1.4 mL, 10 mmol), Pd/C (45 mg, 0.42 mmol), triphenylphosphine(110 mg, 0.42 mmol), and CuI (50 mg, 0.26 mmol). The reaction mixture was stirred at 60 C for 5 h. After cooling, the mixture wasfiltered with celite and the filtrate diluted with dichloromethane,washed with H2O (3 x 40 mL) and dried over MgSO4. After evaporation,the crude product was purified by silica gel chromatography(CH2Cl2). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
65% | With [bis(acetoxy)iodo]benzene; water In acetonitrile at 60℃; for 24h; | 2.1. General procedure for the synthesis of a-hydroxyketonephosphates 3 General procedure: 2.1. General procedure for the synthesis of a-hydroxyketonephosphates 3 To a solution of diarylphosphine oxides 2 (0.5 mmol) inacetonitrile (3.0 mL) were added PhI(OAc)2 (1.25 mmol), H2O(2.0 mmol) and alkynes 1 (0.75 mmol). The reaction mixture wasthen stirred for 24 h at 60 8C in air. After the reaction, thesolvents were removed under vacuum. The residue was puriedby ash chromatography on silica gel using a mixture ofpetroleum ether and ethyl acetate (1:1) as eluent to give thedesired product 3. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With copper(l) iodide; N-ethyl-N,N-diisopropylamine In chloroform at 0 - 20℃; for 24h; Inert atmosphere; Sealed tube; enantioselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
90% | With potassium <i>tert</i>-butylate In dimethyl sulfoxide; <i>tert</i>-butyl alcohol at 80℃; for 12h; Inert atmosphere; stereoselective reaction; | 9 In the reaction flask was added 0.3 mmol of o-methyl phenylacetylene, 0.3 mmol phenylacetonitrile, 0.3 mmol of potassium tert-butoxide, 0.3 mmol of t-butanol, dimethylsulfoxide ml, 80 ° C in a nitrogen after stirring for 12 hours under the protection of the heating and stirring is stopped, cooled to room temperature.The reaction was washed with 15mL water, then extracted three times with ethyl acetate (each with I OmL), combined organic layers were dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and then purified by column chromatography to give the desired product, column chromatography eluent used was a volume ratio of 100: 1 n-hexane and ethyl acetate mixed solvent, 90% yield. |
90% | With potassium <i>tert</i>-butylate; <i>tert</i>-butyl alcohol In dimethyl sulfoxide at 80℃; for 12h; Inert atmosphere; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
72% | With potassium <i>tert</i>-butylate In dimethyl sulfoxide; <i>tert</i>-butyl alcohol at 80℃; for 12h; Inert atmosphere; stereoselective reaction; | 14 In the reaction flask was added 0.3 mmol of o-methyl phenylacetylene, 0.3 mmol p-chlorophenyl acetonitrile, 0.3 mmole of potassium t-butoxide, 0.3 mmol of tert-butyl alcohol, 1 ml of dimethylsulfoxide, at 80 after stirring under nitrogen protection ° C 12 hours to stop the heating and stirring, cooled to room temperature.The reaction was washed with 15mL water, then extracted three times with ethyl acetate (each with IOmL), combined organic layers were dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and then purified by column chromatography to give the desired product, used column chromatography of the eluate volume ratio of 100: 1 n-hexane and ethyl acetate mixed solvent, a yield of 72% |
72% | With potassium <i>tert</i>-butylate; <i>tert</i>-butyl alcohol In dimethyl sulfoxide at 80℃; for 12h; Inert atmosphere; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With potassium <i>tert</i>-butylate In dimethyl sulfoxide; <i>tert</i>-butyl alcohol at 80℃; for 12h; Inert atmosphere; stereoselective reaction; | 15 In the reaction flask was added 0.3 mmol of o-methyl phenylacetylene, 0.3 mmol p-methylphenyl cyanide, 0.3 mmol of potassium tert-butoxide, 0.3 mmol of tert-butyl alcohol, 1 ml of dimethyl sulfoxide, in after stirring at 80 ° C nitrogen protective stop heating and stirring 12 hours, cooled to room temperature.The reaction was washed with 15mL water, then extracted three times with ethyl acetate (each with I OmL), combined organic layers were dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and then purified by column chromatography to give the desired product, column chromatography eluent used was a volume ratio of 100: 1 n-hexane and ethyl acetate mixed solvent, 75% yield. |
75% | With potassium <i>tert</i>-butylate; <i>tert</i>-butyl alcohol In dimethyl sulfoxide at 80℃; for 12h; Inert atmosphere; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
78% | With potassium tert-butylate; In dimethyl sulfoxide; tert-butyl alcohol; at 80℃; for 12h;Inert atmosphere; | In the reaction flask was added 0.3 mmol of o-methyl phenylacetylene, 0.3 mmol of p-tert-butylphenyl acetonitrile, 0.3 mmole of potassium t-butoxide, 0.3 mmol of tert-butyl alcohol, 1 ml of dimethylsulfoxide, after stirring at 80 C nitrogen protective stop heating and stirring 12 hours, cooled to room temperature.The reaction was washed with 15mL water, then extracted three times with ethyl acetate (each with I OmL), combined organic layers were dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and then purified by column chromatography to give the desired product, column chromatography eluent used was a volume ratio of 100: 1 n-hexane and ethyl acetate mixed solvent, a yield of 78% |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
76% | With potassium <i>tert</i>-butylate In dimethyl sulfoxide; <i>tert</i>-butyl alcohol at 80℃; for 12h; Inert atmosphere; stereoselective reaction; | 17 In the reaction flask was added 0.3 mmol of o-methyl phenylacetylene, 0.3 mM 2-naphthylacetonitrile, 0.3 mmol of potassium tert-butoxide, 0.3 mmol of tert-butyl alcohol, 1 ml of dimethylsulfoxide, at 80 after stirring under nitrogen protection ° C 12 hours to stop the heating and stirring, cooled to room temperature.The reaction was washed with 15mL water, then extracted three times with ethyl acetate (each with I OmL), combined organic layers were dried over anhydrous sodium sulfate, the solvent was distilled off under reduced pressure, and then purified by column chromatography to give the desired product, column chromatography eluent used was a volume ratio of 100: 1 n-hexane and ethyl acetate mixed solvent, a yield of 76%. |
76% | With potassium <i>tert</i>-butylate; <i>tert</i>-butyl alcohol In dimethyl sulfoxide at 80℃; for 12h; Inert atmosphere; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
83% | With potassium <i>tert</i>-butylate In dimethyl sulfoxide; <i>tert</i>-butyl alcohol at 80℃; for 12h; Inert atmosphere; stereoselective reaction; | 18 The reaction bottle by adding 0.3 millimoles ofOrtho-methyl phenylacetylene0.3 millimoles of2 - thiophene acetonitrile, 0.3 millimoles of bi Potassium,0.3 millimolar t-butanol, 1 ml of dimethylsulfoxide, and the mixture was stirred for 12 hours under the protection of nitrogen at 80 ° C. After heating and Stirring, cooled to the room temperature. The reaction solution with 15 ml water washing, and then the extraction The ethyl ester three times (once for each 10 ml), the combined organic phase is dried over anhydrous sodium sulfate, the solvent is removed by distillation under reduced pressure, and then purified by column chromatography to obtain the desired product. The column chromatography eluant is the Volume ratio of 100: 1 of the mixed solvent of hexane and yield of 83%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
100% | With copper(II) sulfate; sodium L-ascorbate In water at 20℃; | 2.2. General Synthetic Procedure : Huisgen's 1,3-DipolarCycloaddition of Azides and Alkynes General procedure: Method B: Alkyne (1.00 eq.) and azide (1.00 eq.) weredissolved PEG 400/ H2O (1:1, v/v, 2 mL). Solid CuSO4 wasadded (0.05 eq., 5 mol%) and solid sodium ascorbate (0.10eq., 10 mol %) were added. The reaction mixture was allowedto stir at room temperature for 1-8h. After the reactionwas complete, as indicated by TLC, the reaction mixture wasdiluted with water and filtered at the pump to collect theproduct or extracted with ethyl acetate (3 2 ml). The organiclayer was dried over anhydrous sodium sulfate anddistilled using rotary vacuum evaporator. The afforded crudeproduct was recrystallized from cyclohexane. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With 1,1'-bis-(diphenylphosphino)ferrocene; (hydridotris(1-pyrazolyl)borato)(1,5-cyclooctadiene)rhodium(I) In acetonitrile at 110℃; for 12h; Inert atmosphere; Glovebox; Sealed tube; stereoselective reaction; | |
79% | With 1,1'-bis-(diphenylphosphino)ferrocene; (hydridotris(1-pyrazolyl)borato)(1,5-cyclooctadiene)rhodium(I) In acetonitrile at 110℃; for 12h; Inert atmosphere; Sealed tube; Glovebox; stereoselective reaction; | (E)-3-(o-tolyl)acrylonitrile (2k) In an anhydrous, argon-filled glovebox, a 4 ml. vial was charged with TpRh(COD) (6.3 mg, 15 μηιοΙ, 7.5 mol%), dppf (8.3 mg, 15 μηιοΙ, 7.5 mol%), and MeCN (1 .0 ml_, c = 0.2 M). 1 - Ethynyl-2-methylbenzene (23.2 mg, 21 .2 μΙ_, 0.200 mmol, 1.00 equiv) and acetone cyanohydrin (17.0 mg, 19.5 μΙ_, 0.200 mmol, 1.00 equiv) were then added to the reaction mixture. The vial was sealed with a Teflon cap and moved from the glovebox to a preheated metal heating block (1 10 °C). The reaction mixture was then stirred at 1 10 °C for 12 hours. After cooling to 23 °C, the resulting mixture was filtered through a short plug of silica gel, eluting with EtOAc. The filtrate was collected and concentrated in vacuo. The resulting residue was purified by flash column chromatography on silica gel, eluting with EtOAc/hexane 1 :10 (v/v) to afford 22.6 mg (79%) of the title compound as pale yellow liquid.Rf = 0.45 (EtOAc/hexanes 1 :10 (v/v)).NMR Spectroscopy:1H NMR (500 MHz, CDCI3, 23 °C, δ): 7.70 (d, J = 16.5 Hz, 1 H), 7.46 (d, J = 7.4 Hz, 1 H), 7.33 (dd, J = 8.1 , 7.4 Hz, 1 H), 7.23 (dd, J = 7.7, 7.4 Hz, 2H), 5.80 (d, J = 16.5 Hz, 1 H), 2.41 (s, 3H).13C NMR (125 MHz, CDCI3, 23 °C, δ): 148.4, 137.2, 132.5, 131 .0, 130.9, 126.6, 125.5, 1 18.3, 97.2, 19.6.HRMS-FIA (m/z) calc'd for C10H9N [M]+, 143.0732; found: 143.0729. |
Tags: 766-47-2 synthesis path| 766-47-2 SDS| 766-47-2 COA| 766-47-2 purity| 766-47-2 application| 766-47-2 NMR| 766-47-2 COA| 766-47-2 structure
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P336 | Thaw frosted parts with lukewarm water. Do not rub affected area. |
P337 | If eye irritation persists: |
P338 | Remove contact lenses, if present and easy to do. Continue rinsing. |
P340 | Remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P341 | If breathing is difficult, remove victim to fresh air and keep at rest in a position comfortable for breathing. |
P342 | If experiencing respiratory symptoms: |
P350 | Gently wash with plenty of soap and water. |
P351 | Rinse cautiously with water for several minutes. |
P352 | Wash with plenty of soap and water. |
P353 | Rinse skin with water/shower. |
P360 | Rinse immediately contaminated clothing and skin with plenty of water before removing clothes. |
P361 | Remove/Take off immediately all contaminated clothing. |
P362 | Take off contaminated clothing and wash before reuse. |
P363 | Wash contaminated clothing before reuse. |
P370 | In case of fire: |
P371 | In case of major fire and large quantities: |
P372 | Explosion risk in case of fire. |
P373 | DO NOT fight fire when fire reaches explosives. |
P374 | Fight fire with normal precautions from a reasonable distance. |
P376 | Stop leak if safe to do so. Oxidising gases (section 2.4) 1 |
P377 | Leaking gas fire: Do not extinguish, unless leak can be stopped safely. |
P378 | |
P380 | Evacuate area. |
P381 | Eliminate all ignition sources if safe to do so. |
P390 | Absorb spillage to prevent material damage. |
P391 | Collect spillage. Hazardous to the aquatic environment |
P301 + P310 | IF SWALLOWED: Immediately call a POISON CENTER or doctor/physician. |
P301 + P312 | IF SWALLOWED: call a POISON CENTER or doctor/physician IF you feel unwell. |
P301 + P330 + P331 | IF SWALLOWED: Rinse mouth. Do NOT induce vomiting. |
P302 + P334 | IF ON SKIN: Immerse in cool water/wrap in wet bandages. |
P302 + P350 | IF ON SKIN: Gently wash with plenty of soap and water. |
P303 + P361 + P353 | IF ON SKIN (or hair): Remove/Take off Immediately all contaminated clothing. Rinse SKIN with water/shower. |
P304 + P312 | IF INHALED: Call a POISON CENTER or doctor/physician if you feel unwell. |
P304 + P340 | IF INHALED: Remove victim to fresh air and Keep at rest in a position comfortable for breathing. |
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 |
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