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CAS No. : | 133745-75-2 | MDL No. : | MFCD00144885 |
Formula : | C12H10FNO4S2 | Boiling Point : | - |
Linear Structure Formula : | - | InChI Key : | RLKHFSNWQCZBDC-UHFFFAOYSA-N |
M.W : | 315.34 | Pubchem ID : | 588007 |
Synonyms : |
|
Num. heavy atoms : | 20 |
Num. arom. heavy atoms : | 12 |
Fraction Csp3 : | 0.0 |
Num. rotatable bonds : | 4 |
Num. H-bond acceptors : | 6.0 |
Num. H-bond donors : | 0.0 |
Molar Refractivity : | 70.29 |
TPSA : | 88.28 Ų |
GI absorption : | High |
BBB permeant : | No |
P-gp substrate : | No |
CYP1A2 inhibitor : | No |
CYP2C19 inhibitor : | Yes |
CYP2C9 inhibitor : | Yes |
CYP2D6 inhibitor : | No |
CYP3A4 inhibitor : | No |
Log Kp (skin permeation) : | -6.4 cm/s |
Log Po/w (iLOGP) : | 2.26 |
Log Po/w (XLOGP3) : | 2.57 |
Log Po/w (WLOGP) : | 4.53 |
Log Po/w (MLOGP) : | 0.9 |
Log Po/w (SILICOS-IT) : | 0.19 |
Consensus Log Po/w : | 2.09 |
Lipinski : | 0.0 |
Ghose : | None |
Veber : | 0.0 |
Egan : | 0.0 |
Muegge : | 0.0 |
Bioavailability Score : | 0.55 |
Log S (ESOL) : | -3.59 |
Solubility : | 0.0803 mg/ml ; 0.000255 mol/l |
Class : | Soluble |
Log S (Ali) : | -4.07 |
Solubility : | 0.0267 mg/ml ; 0.0000847 mol/l |
Class : | Moderately soluble |
Log S (SILICOS-IT) : | -4.36 |
Solubility : | 0.0137 mg/ml ; 0.0000435 mol/l |
Class : | Moderately soluble |
PAINS : | 0.0 alert |
Brenk : | 1.0 alert |
Leadlikeness : | 0.0 |
Synthetic accessibility : | 2.97 |
Signal Word: | Warning | Class: | N/A |
Precautionary Statements: | P501-P202-P201-P264-P280-P302+P352-P308+P313-P337+P313-P305+P351+P338-P362+P364-P332+P313-P405 | UN#: | N/A |
Hazard Statements: | H315-H319-H341 | Packing Group: | N/A |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With n-butyllithium; In hexane; | B. Synthesis of (tert-butyl)[(5-chloro-3-fluoro(2-thienyl))sulfonyl]amine A THF solution (1.5 mL) of 128 mg (0.50 mmol) of <strong>[155731-14-9](tert-butyl)[(5-chloro(2-thienyl))sulfonyl]amine</strong> was cooled to -78 C. and treated with 954 muL (1.5 mmol) of a 1.6 M solution of butyl lithium in hexane. After 1 h, 159 mg (0.5 mmol) of bis(phenylsulfonyl)fluoroamine was added and the solution was allowed to warm to 23 C. The reaction was quenched with 1 mL of sat. NH4Cl, extracted 3 times with diethyl ether, dried (MgSO4), concentrated in vacuo to afford a quantitative yield (147 mg) of the desire product. 19F-NMR (CDCl3) delta(ppm): -113.4. | |
With n-butyllithium; In hexane; | B. Synthesis of (tert-butyl)[(5-chloro-3-fluoro(2-thienyl))sulfonyl]amine A THF solution (1.5 mL) of 128 mg (0.50 mmol) of <strong>[155731-14-9](tert-butyl)[(5-chloro(2-thienyl))sulfonyl]amine</strong> was cooled to -78 C. and treated with 954 muL (1.5 mmol) of a 1.6 M solution of butyl lithium in hexane. After 1 h, 159 mg (0.5 mmol) of bis(phenylsulfonyl)fluoroamine was added and the solution was allowed to warm to 23 C. The reaction was quenched with 1 mL of sat. NH4Cl, extracted 3 times with diethyl ether, dried (MgSO4), concentrated in vacuo to afford a quantitative yield (147 mg) of the desire product. 19F-NMR (CDCl3) delta (ppm): -113.4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trifluorormethanesulfonic acid; hydrogen bromide; acetic acid; In hexane; ethyl acetate; | Preparation 29 6-Fluoro-7-hydroxychroman-4-one A mixture of 1,3-dimethoxybenzene (3.80 mL, 29.0 mmol) and N-fluorodibenzenesulfonamide (4.21 g, 29.21 mmol) was heated at 60 C. overnight. The mixture was cooled and flash chromatographed on silica gel (2*5 inches packed in hexane) with elution proceeding as follows: 3% ethyl acetate/hexane (1000 mL), discarded forerun; 3% ethyl acetate/hexane (1000 mL), 2.69 g of a 2:1 mixture of 2,4-dimethoxyfluorobenzene and starting material which was carried directly into the next step. The product of the above reaction was combined with acetic acid (11 mL) and 48% HBr (11 mL) and refluxed 3 h. The reaction was concentrated and flash chromatographed on silica gel (2*5 inches packed in hexane) with elution proceeding as follows: 10% ethyl acetate/hexane (2000 mL), 0.95 g (43%) of <strong>[103068-41-3]2,4-dihydroxyfluorobenzene</strong> as a waxy white solid which was used without purification. A mixture of <strong>[103068-41-3]2,4-dihydroxyfluorobenzene</strong> (0.15 g, 1.17 mmol), 3-chloropropionic acid (0.13 g, 1.20 mmol) and trifluoromethanesulfonic acid (1 mL) were heated to 80 C. for 3 h. The reaction was poured into water and extracted with ether (3*). The combined organic phase was washed with water and brine, dried over magnesium sulfate, and concentrated to give 2,4-dihydroxy-5-fluoro-beta-chloropropiophenone as a red solid which had: NMR delta 7.37 (d, J=10.8 Hz, 1 H), 6.54 (d, J=7.7 Hz, 1 H), 3.87 (t, J=6.8 Hz, 2 H) 3.33 (t, J=6.8 Hz, 2 H). This product still contained some residual 3-chloropropionic acid but was suitable for use in the next reaction. | |
With trifluorormethanesulfonic acid; hydrogen bromide; acetic acid; In hexane; ethyl acetate; | Preparation 29 6-Fluoro-7-hydroxychroman-4-one A mixture of 1,3-dimethoxybenzene (3.80 mL, 29.0 mmol) and N-fluorodibenzenesulfonamide (4.21 g, 29.21 mmol) was heated at 60 C. overnight. The mixture was cooled and flash chromatographed on silica gel (2*5 inches packed in hexane) with elution proceeding as follows: 3% ethyl acetate/hexane (1000 mL), discarded forerun; 3% ethyl acetate/hexane (1000 mL), 2.69 g of a 2:1 mixture of 2,4-dimethoxyfluorobenzene and starting material which was carried directly into the next step. The product of the above reaction was combined with acetic acid (11 mL) and 48% HBr (11 mL) and refluxed 3 h. The reaction was concentrated and flash chromatographed on silica gel (2*5 inches packed in hexane) with elution proceeding as follows: 10% ethyl acetate/hexane (2000 mL), 0.95 g (43%) of <strong>[103068-41-3]2,4-dihydroxyfluorobenzene</strong> as a waxy white solid which was used without purification. A mixture of <strong>[103068-41-3]2,4-dihydroxyfluorobenzene</strong> (0.15 g, 1.17 mmol), 3-chloropropionic acid (0.13 g, 1.20 mmol) and trifluoromethanesulfonic acid (1 mL) were heated to 80 C. for 3 h. The reaction was poured into water and extracted with ether (3x). The combined organic phase was washed with water and brine, dried over magnesium sulfate, and concentrated to give 2,4-dihydroxy-5-fluoro-beta-chloropropiophenone as a red solid which had: NMR delta7.37 (d, J=10.8 Hz, 1 H), 6.54 (d, J=7.7 Hz, 1 H), 3.87 (t, J=6.8 Hz, 2 H), 3.33 (t, J=6.8 Hz, 2 H). This product still contained some residual 3-chloropropionic acid but was suitable for use in the next reaction. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
47% | With hydrogenchloride; In dichloromethane; | EXAMPLE 5 This Example is directed to the fluorination of trimethylsilyloxycyclohexene ((CH3)3 SiOC6 H9) to form 2-fluorocyclohexanone (C6 H9 FO). A solution of 5 millimoles trimethyl-silyloxycyclohexene in 10 milliliters dichloromethane was dropped into a solution of 6 millimoles N-fluorobenzenesulfonimide prepared according to Example 1 above in 15 milliliters dichloromethane. The mixture was stirred for 24 hours at room temperature. 60 milliliters 0.1N hydrogen chloride were poured into the mixture and stirring was continued for 10 minutes. The mixture was extracted with dichloromethane and the organic layers were washed with water and brine. A 47% yield of 2-fluorocyclohexanone was obtained. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With acetic acid; In tetrahydrofuran; water; pentane; | 49. Preparation of t-Butyl N-(4-Fluoro-2-methoxy-3-pyridinyl)carbamate To a solution of 8 g (35.7 mmol) of t-butyl N-(2-methoxy-3-pyridyl)carbamate in 200 mL of dry tetrahydrofuran was added with stirring at -60 C., 46.2 mL (78.5 mmol) of 1.7M t-butyl lithium in pentane. The resulting solution was allowed to warm slowly with stirring to -20 C. over a 20 to 30 min period. It was then cooled to about -60 C. and 12.2 g (38.7 mmol) of N-fluorodibenzenesulfonimide was added with stirring all at once. The mixture was allowed to warm to -20 C. and was poured into 500 mL of ether. The resulting ethereal solution was washed with a mixture of 2.5 g (41.7 mmol) of acetic acid and 150 mL of water. The aqueous phase was extracted with 200 mL of ether. The ethereal extracts were combined, dried over magnesium sulfate, filtered, and concentrated by evaporation. The residue was purified by flash chromatography to obtain 6.7 g (77 percent of theory) of the title compound as a colorless solid melting at 75-77 C. Elemental Analysis C11 H15 FN2 O3 Calc.: %C, 54.5; %H, 6.24; %N, 11.6 Found: %C, 54.2; %H, 6.39; %N, 11.4 1 H NMR (CDCl3): 7.88 (dd, 1H, j=5.8, 7.6); 6.68 (dd, 1H, j=5.8, 8.9); 5.9 (br, 1H); 3.9 (s, 3H); 1.45 (s, 9H). | |
With acetic acid; In tetrahydrofuran; water; pentane; | 9. Preparation of t-butyl N-(4-Fluoro-2-methoxy-3-pyridinyl)carbamate To a solution of 8 g (35.7 mmol) of t-butyl N-(2-methoxy-3-pyridyl)carbamate in 200 mL of dry tetrahydrofuran was added with stirring at -60 C., 46.2 mL (78.5 mmol) of 1.7M t-butyl lithium in pentane. The resulting solution was allowed to warm slowly with stirring to -20 C. over a 20 to 30 min period. It was then cooled to about -60 C. and 12.2 g (38.7 mmol) of N-fluorodibenzenesulfonimide was added with stirring all at once. The mixture was allowed to warm to -20 C. and was poured into 500 mL of ether. The resulting ethereal solution was washed with a mixture of 2.5 g (41.7 mmol) of acetic acid and 150 mL of water. The aqueous phase was extracted with 200 mL of ether. The ethereal extracts were combined, dried over magnesium sulfate, filtered, and concentrated by evaporation. The residue was purified by flash chromatography to obtain 6.7 g (77 percent of theory) of the title compound as a colorless solid melting at 75-77 C. Elemental Analysis C11 H15 FN2 O3 Calc.: %C, 54.5; %H, 6.24; %N, 11.6 Found: %C, 54.2; %H, 6.39; %N, 11.4. 1 H NMR (CDCl3): 7.88 (dd, 1H, j=5.8, 7.6); 6.68 (dd, 1H, j=5.8, 8.9); 5.9 (br, 1H); 3.9 (s, 3H); 1.45 (s, 9H |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With n-butyllithium; In tetrahydrofuran; hexane; ethyl acetate; | EXAMPLE 61 (+,-)-N-(cis-2-(3,6-dimethoxy-2-fluorophenyl)-cyclopropyl)-N'-(5-chloropyrid-2-yl)-urea To a solution of 1,4-dimethoxybenzene (15.0 g, 0.109 mol) in 300 mL of dry THF was added 2.5M n-butyllithium (45.6 mL, 0.114 mol) at room temperature under nitrogen. After addition was complete, the solution was stirred for 1 hr. The mixture was cooled to -70 C. and N-fluorobenzenesulfonimide (36.0 g, 0.114 mol) in 150 mL of THF was added slowly, keeping the temperature below -60 C. The solution was allowed to warm to room temperature during the night. 100 mL of NH4 Cl (sat) was added and the mixture was extracted with diethyl ether/THF. The organic phase was washed with 1M NaOH (2*60 mL), dried over MgSO4 and evaporated. Column chromatography (silica gel, n-hexane followed by 1, 5 and 10% EtOAc in n-hexane) provided 11.43 g of a mixture of 1,4-dimethoxy-2-fluorobenzene and 1,4-dimethoxybenzene (4.3:1). This mixture was reacted in a manner analogous to Examples 362, 375 and 348 of WO 93/03022 to give (+,-)-cis-2-(3,6-dimethoxy2-fluorophenyl) cyclopropylamine. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With n-butyllithium; diisopropylamine; In tetrahydrofuran; hexane; ethyl acetate; | 4-Chloro-3-fluoro-6-methoxyquinoline 1.3 cm3 of diisopropylamine in 50 cm3 of tetrahydrofuran were cooled to a temperature in the region of -75° C. and 5.8 cm3 of a 1.6 M solution of butyl lithium in hexane were added, with stirring and under an inert atmosphere. After stirring for 20 minutes at a temperature in the region of -75° C., a solution of 1.2 g of <strong>[4295-04-9]4-chloro-6-methoxyquinoline</strong> in 20 cm3 of tetrahydrofuran was added. The solution obtained was stirred for a further 4 hours, followed by addition of a solution of 2.9 g of N-fluorobenzene sulfonimide in 10 cm3 of tetrahydrofuran. After stirring for 2 hours at a temperature in the region of 20° C., the reaction mixture was hydrolyzed with 200 cm3 of a 90/10 tetrahydrofuran/water mixture and then 100 cm3 of a saturated sodium chloride solution and 150 cm3 of ethyl acetate. The mixture was washed with 3 times 80 cm3 of a saturated sodium chloride solution, dried over magnesium sulfate, filtered and concentrated to dryness under reduced pressure (2 kPa) at a temperature in the region of 40° C. The residue obtained was purified by chromatography, under atmospheric pressure, on a column of silica gel (particle size 70-200 mu; diameter 4 cm; mass 100 g), eluding with dichloromethane. The fractions containing the product were combined and then concentrated to dryness under reduced pressure (5 kPa) at a temperature in the region of 40° C. 0.4 g of 4-chloro-3-fluoro-6-methoxyquinoline was obtained. 1H NMR Spectrum (300 MHz, (CD3)2SO-d6, delta in ppm) 4.01 (s: 3H); 7.43 (d, J=2.5 Hz: 1H); 7.52 (dd, J=9 and 2.5 Hz: 1H); 8.07 (d, J=9 Hz: 1H); 8.91 (d, J=1 Hz: 1H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With hydrogenchloride; In tetrahydrofuran; | D. Preparation of 3-Fluoro-2-thiophenecarboxylic Acid (14) 2-Thiophene-carboxylic acid (1.7 g, 13.3 mmol) was dissolved in anhydrous THF (30 mL) and the solution was cooled to -78 C. under Ar, with stirring. n-Butyllithium (18.3 mL, 29.3 mmol) in hexanes was added to the above solution and the mixture was stirred for 30 min. A solution of N-fluorobenzenesulfonimide (5 g, 15.9 mmol) in THF (30 mL) was then added and the resulting solution was stirred at -78 C. for 4 h and allowed to warm to ambient temperature over a period of 6 h. The reaction was diluted with diethyl ether (100 mL), cooled to 0 C., and 1 N HCl (15 mL) was added to give a biphasic mixture. The aqueous layer was isolated and washed with diethyl ether (3*50 mL). The combined ethereal layers were dried over MgSO4, filtered, and concentrated in vacuo to yield an orange oil. The oil was subjected to column chromatography on silica gel using 1:1 hexanes/ethyl acetate as the eluent. (14) was obtained as a slightly brown solid (0.777 g) in 40% yield. TLC (1:1 ethyl acetate/hexanes) Rf 0.17; 1H NMR (CDCl3) delta 10.7 (s, 1H), 7.53 (dd, J=5.4, 3.6 Hz, 1H), 6.89 (d, J=5.4 Hz, 1H); 13C NMR (75 MHz, CDCl3) delta 166.2 (d, J=3.5 Hz), 161.5 (d, J=278 Hz), 132.0 (d, J=10 Hz), 118.9 (d, J=24.7 Hz), 113.6; 19FNMR (282 MHz, CDCl3, CFCl3) delta-65.2 (d, J=6 Hz); EI-MS m/e 145.9838 (M+ calcd 145.9838 for C5H3FO2S). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
Ethyl 3-fluoro- 1 -(4-methoxybenzyl)- 1 H-pyrazole-4-carboxylate and ethyl l-(4- methoxybenzyl)-3-(phenylsulfonyl)-lH-pyrazole-4-carboxylateAccording to Scheme 10: The reaction was done following the general procedure described for Eample 9 using ethyl 1 -(4-methoxybenzyl)- lH-pyrazole-4-carboxylate (3.84 mmol, 1.00 g) as starting material and N-fluoro-N- (phenylsulfonyl)benzenesulfonamide (3.84 mmol, 1.21 g) as electrophile. The resulting crude product was purified by flash chromatography over silica gel using cyclohexane/ AcOEt (90:10) as eluent to yield after evaporation a mixture of ethyl 3- fluoro-l-(4-methoxybenzyl)-lH-pyrazole-4-carboxylate and ethyl l-(4- methoxybenzyl)-3-(phenylsulfonyl)-lH-pyrazole-4-carboxylate (330 mg, 50/50). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
To a solution of LDA [freshly prepared from BuLi (1.6M solution in hexanes,5.14 mL, 8.22 mmol) and diisopropylamine (1.44 mL, 10.39 mmol) in tetrahydrofuran (6 mL) at 0 C] was added dropwise a solution of 1-tert-butyl 3-methyl piperidine-1,3- dicarboxylate (2 g, 8.22 mmol) in tetrahydrofuran (8 mL) at 0 C. The solution was stirred at 0 C for 30 min and then transfered to a 0 C solution of N- fluorobenzenesulfonimide (3.24 g, 10.28 mmol) in tetrahydrofuran (12 mL). The reaction mixture was stirred at 0 C for 15 min and then at room temperature for -20 hrs. The total solvent volume was reduced under reduced pressure to approximately one third and EtOAc was added. The mixture was washed with water, 0.1N aqueoushydrochloride solution, saturated aqueous sodium bicarbonate solution and brine. The organic phase was dried over sodium sulfate, filtered off and concentrated under reduced pressure. The crude was suspended in EtOAc and decanted. The filtrate wasconcentrated under reduced pressure and purified by column chromatography [silica gel, 80 g, EtOAc/heptane = 0/100 to 50/50] providing 1-tert-butyl 3-methyl (3- fluoropiperidine)-l,3-dicarboxylate (775 mg) as a colorless liquid. LCMS (m/z): 262.1 [M+H]+, 206.1 [M+H, loss of t-Bu]+; Rt = 0.86 min. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
The mixture of benzenesulfonimides (compound 4) (19.6 mmol)and 2% sodium hydroxide aqueous solution (350 mL, 175 mmol)was stirred for 20 min, the precipitate was filtered and the solidbenzenesulfonimide sodium salt (compound 5) was air-dried. Themixture of compound 5 and acetonitrile (150 mL) was stirred andcooled to 30 C. A 5e8 L gaseous mixture of 10% F2 in nitrogen(volume percent) was introduced at a rate of 150 mL/min to thesolution. The insoluble solid was removed by filtration. The filtratewas evaporated under vacuum and washed with water, a yellowsolid was obtained. After recrystallization pure compound 1 wasafforded. 4.2.1 N-Fluoro-p-fluorobenzenesulfonimde (1b) White crystal. mp 114.8-116.0 C; 1H NMR (CDCl3, 400 MHz) delta 8.08-8.05 (m, 4H), 7.33-7.29 (m, 4H); 19F NMR (CDCl3, 376 MHz) delta -36.42 (s, 1F), -98.36 (s, 2F). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With 3-fluoro-1-nitrobenzene; C20H28N4O2Pd(2+)*2CF3O3S(1-); In [D3]acetonitrile; at 50℃;Inert atmosphere;Kinetics; | This experiment was carried out under an N2 atmosphere. A 0.167 M solution of NFBS in CD3CN was prepared in a vial and sealed with a septum cap. In five separate septum-sealed screw cap NMR tubes, solutions of 1 (1.25, 2.5, 3.75, 5.0, and 10 muiotaetaomicron) and 3- nitro-fluorobenzene (0.019-0.038 muiotaetaomicron) in 0.200 mL CD3CN were prepared in the following way: 1.25 and 2.50 mutauetaomicron reactions: A stock solution of 3.8 mg 1 (5.0 muiotaetaomicron) and 8.0 of 3-nitrofluorobenzene (0.076 mutauetaomicron) in 0.400 mL CD3CN was prepared. To one NMR tube (1.25 muiotaetaomicron 1) was added 0.100 mL of the stock solution and 0.100 mL pure CD CN. To the other tube (2.5 muiotaetaomicron 1) was added 0.200 mL of the stock solution. [00278] 3.75 and 5.0 muetatauomicron reactions: A stock solution of 7.6 mg 1 (10 muiotaetaomicron) in 0.400 mL CD CN was prepared. To one NMR tube (3.75 muiotaetaomicron 1) was added 0.150 mL of the stock solution, 4.0 mu^ (0.038 muiotaetaomicron) 3-nitrofluorobenzene, and 0.050 mL pure CD CN. To the other tube (5.0 muiotaetaomicron 1) was added 0.200 mL of the stock solution and 4.0 mu^ (0.038 muiotaetaomicron) 3- nitrofluorobenzene . [00279] 10 muetaiotaomicron reaction: A solution of 7.6 mg (10 mutauetaomicron) 1 and and 4.0 mu (0.038 mutauetaomicron) 3-nitrofluorobenzene in 0.200 mL CD CN was prepared in an NMR tube. [00280] For each reaction, 0.300 mL of the NFBS solution was added to the NMR tube via syringe, the sample was immediately inserted into the NMR probe pre-heated at 50 C, and the consumption of NFBS was followed by integration of the 19F NMR spectra with 3-nitrofluorobenzene. The reactions were followed over 15-30% conversion, except the last one (10.0 muiotaetaomicron 1), which was followed through 90% conversion (>3 half-lives). The plot of ln[NFBS] vs. time shows excellent linearity throughout, indicating an overall reaction order of unity. Pseudo-first-order analysis was therefore applied to determine the dependence of k0bs on [1]. A plot of vs ln[l] reveals a first order dependence on [1]. The overall rate law is therefore rate = fc[l][NFBS]. A plot of k0bs vs. [1] revealed a slope of 1.26xl0"2 M_1s_1, which is the value of k. The results are shown in Figure 4. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
61% | With [Ag(2,2'-bipyridine)2](ClO4); C20H28N4O2Pd(2+)*2CF3O3S(1-); In acetonitrile; at 23℃; for 24h;Inert atmosphere; Sealed tube; | Under N2 atmosphere, an oven-dried 4 mL vial was charged with l-methoxy-4- (trifluoromethoxy)benzene (57.6 mg, 45.5 mu, 0.300 mmol, 1.00 equiv), palladium complex 1 (11.4 mg, 15.0 muetaiotaomicron, 5.00 mol ), Ag(bipy)2C104 (16.0 mg, 30.0 muetaiotaomicron, 10.0 mol ), and NFBS (0.189 g, 0.600 mmol, 2.00 equiv). Acetonitrile (0.75 mL, c = 0.40 M) was added and the reaction mixture was stirred in a sealed vial at 23 C for 24 h. Subsequently, triethylamine (30.5 mg, 42.0 mu, 0.300 mmol, 1.00 equiv) was added and the reaction mixture was concentrated in vacuo. The residue was purified by chromatography on silica gel, eluting with hexanes/EtOAc (19: 1 to 4: 1 (v/v) with 1% triethylamine), to afford 89.2 mg of the title compound as a colorless solid (61 yield). [00215] Rf = 0.30 (hexanes/EtOAc 4: 1 (v/v)). NMR Spectroscopy: 1H NMR (600 MHz, CDC13, 23 C, delta): 7.97 (d, J = 7.6 Hz, 4H), .65-1.69 (m, 2H), 7.54 (t, J = 7.6 Hz, 4H), 7.29 (dd, J = 9.5, 2.9 Hz, 1H), 6.95 (d, J = 2.9 Hz, 1H), 6.85 (d, J = 8.6 Hz, 1H), 3.43 (s, 3H). 13C NMR (125 MHz, CDC13, 23 C, delta): 156.8, 141.8, 139.8, 134.0, 128.9, 128.9, 126.5, 125.1, 123.4, 120.6 (q, J = 255 Hz), 112.4, 55.8. 19F NMR (375 MHz, CDC13, 23 C, delta): -59.9. Mass Spectrometry: HRMS (ESI-TOF) (m/z): calcd for C20H2oF3N206S2 [M + NH4]+, 505.0709, found, 505.0721. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | With [Ag(2,2'-bipyridine)2](ClO4); C20H28N4O2Pd(2+)*2CF3O3S(1-); In acetonitrile; at 4℃; for 24h;Inert atmosphere; Sealed tube; | Under N2 atmosphere, an oven-dried 4 mL vial was charged with <strong>[22913-24-2]methyl benzo[b]thiophene-2-carboxylate</strong> (27.7 mg, 0.300 mmol, 1.00 equiv), palladium complex 1 (11.4 mg, 15.0 mupiiotaomicron, 5.00 mol%), Ag(bipy)2C104 (16.0 mg, 30.0 mupiiotaomicron, 10.0 mol%), and NFBS (0.189 g, 0.600 mmol, 2.00 equiv). Acetonitrile (0.75 mL, c = 0.40 M) was added and the reaction mixture was stirred in a sealed vial at 4 C for 24 h. Subsequently, triethylamine (30.5 mg, 42.0 mu, 0.300 mmol, 1.00 equiv) was added and the reaction mixture was concentrated in vacuo. The residue was purified by chromatography on silica gel, eluting with hexanes/EtOAc (19: 1 to 4: 1 (v/v) with 1% triethylamine), to afford 115 mg of the title compound as a colorlesssolid (79% yield). [00237] R/= 0.38 (hexanes/EtOAc 7:3 (v/v)). NMR Spectroscopy: 1H NMR (600 MHz, CDC13, 23 C, delta): 7.98-8.00 (m, 4H), 7.83 (d, J = 8.2 Hz, 1H), 7.66-7.70 (m, 2H), 7.53 (t, J = 7.9 Hz, 4H), 7.46 (td, J = 1.6, 1.2 Hz, 1H), 7.30-7.33 (m, 1H), 7.25-7.28 (m, 1H), 3.39 (s, 3H). 13C NMR (125 MHz, CDC13, 23 C, delta): 160.9, 139.8, 138.2, 137.4, 134.6, 134.2, 129.4, 128.9, 128.8, 127.8, 125.4, 124.8, 122.8, 52.3. Mass Spectrometry: HRMS (ESI-TOF) (m/z): calcd for C22H2iN206S3 [M + NH4]+, 505.0556, found, 505.0569. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
84% | With [Ag(2,2'-bipyridine)2](ClO4); C20H28N4O2Pd(2+)*2CF3O3S(1-); In acetonitrile; at 23℃; for 24h;Inert atmosphere; Sealed tube; | Under N2 atmosphere, an oven-dried 4 mL vial was charged with thiophene-2- carbonitrile (27.9 mu, 32.7 mg, 0.300 mmol, 1.00 equiv), palladium complex 1 (11.4 mg, 15.0 muetaiotaomicron, 5.00 mol ), Ag(bipy)2C104 (16.0 mg, 30.0 muetaiotaomicron, 10.0 mol ), and NFBS (0.189 g, 0.600 mmol, 2.00 equiv). Acetonitrile (0.75 mL, c = 0.40 M) was added and the reaction mixture was stirred in a sealed vial at 23 C for 24 h. Subsequently, triethylamine (30.5 mg, 42.0 mu, 0.300 mmol, 1.00 equiv) was added and the reaction mixture was concentrated in vacuo. The residue was purified by chromatography on silica gel, eluting with hexanes/EtOAc (19: 1 to 4: 1 (v/v) with 1% triethylamine), to afford 102 mg of the title compound as a colorlesssolid (84% yield). [00243] R/= 0.41 (hexanes/EtOAc 3:2 (v/v)). NMR Spectroscopy: 1H NMR (600 MHz, CDC13, 23 C, delta): 7.97 (d, / = 7.6 Hz, 4H), 7.74 (t, / = 7.6 Hz, 2H), 7.60 (t, / = 7.9 Hz, 4H), 7.46 (d, / = 4.1 Hz, 1H), 6.77 (d, / = 4.1 Hz, 1H). 13C NMR (100 MHz, CDC13, 23 C, delta): 140.3, 138.1, 135.8, 135.0, 131.6, 129.5, 128.9, 113.2, 112.6. Mass Spectrometry: HRMS (ESI-TOF) (m/z): calcd for C17H12N2Na04S3 ([M + Na]+), 426.9851, found, 426.9861. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
52% | With [Ag(2,2'-bipyridine)2](ClO4); C20H28N4O2Pd(2+)*2CF3O3S(1-); In acetonitrile; at 4℃; for 24h;Inert atmosphere; Sealed tube; | Under N2 atmosphere, an oven-dried 4 mL vial was charged with 1 -(1 -methyl- 1H- pyrrol-2-yl)ethanone (36.9 mg, 35.5 mu, 0.300 mmol, 1.00 equiv), palladium complex 1 (11.4 mg, 15.0 muetaiotaomicron, 5.00 mol%), Ag(bipy)2C104 (16.0 mg, 30.0 muetaiotaomicron, 10.0 mol%), and NFBS (0.189 g, 0.600 mmol, 2.00 equiv). Acetonitrile (0.75 mL, c = 0.40 M) was added and the reaction mixture was stirred in a sealed vial at 4 C for 24 h. Subsequently, triethylamine (30.5 mg, 42.0 mu, 0.300 mmol, 1.00 equiv) was added and the reaction mixture was concentrated in vacuo. The residue was purified by chromatography on silica gel, eluting with hexanes/EtOAc (19: 1 to 3: 1 (v/v) with 1% triethylamine), to afford 65.8 mg of the title compound as a colorless solid (52% yield). [00247] Rf = 0.46 (hexanes/EtOAc 3:2 (v/v)). NMR Spectroscopy: 1H NMR (600 MHz, CDCI3, 23 C, delta): 7.90-7.94 (m, 4H), 7.68-7.72 (m, 2H), 7.56 (t, J = 8.2 Hz, 4H), 6.89 (d, J = 4.7 Hz, 1H), 5.92 (d, J = 4.1 Hz, 1H), 3.42 (s, 3H), 2.44 (s, 3H). 13C NMR (125 MHz, CDC13, 23 C, delta): 189.1, 138.7, 134.7, 131.4, 129.3, 128.9, 127.5, 117.5, 111.4, 33.1, 27.3. Mass Spectrometry: HRMS (ESI-TOF) (m/z): calcd for C19Hi9N205S2 ([M + H]+), 419.0730, found, 419.0734 |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
55%; 31% | With [Ag(2,2'-bipyridine)2](ClO4); C20H28N4O2Pd(2+)*2CF3O3S(1-); In acetonitrile; at 23℃; for 24h;Inert atmosphere; Sealed tube; | Under N2 atmosphere, an oven-dried 4 mL vial was charged 2-chloro-4- methoxypyridine (43.1 mg, 34.2 mu, 0.300 mmol, 1.00 equiv), palladium complex 1 (11.4 mg, 15.0 mupiiotaomicron, 5.00 mol%), Ag(bipy)2C104 (16.0 mg, 30.0 mupiiotaomicron, 10.0 mol%), and NFBS (0.189 g, 0.600 mmol, 2.00 equiv). Acetonitrile (0.75 mL, c = 0.40 M) was added and the reaction mixture was stirred in a sealed vial at 23 C for 24 h. Subsequently, triethylamine (30.5 mg, 42.0 mu, 0.300 mmol, 1.00 equiv) was added and the reaction mixture was concentrated in vacuo. The residue was purified by chromatography on silica gel, eluting with hexanes/EtOAc (7:3 to 2:3 (v/v) with 1% triethylamine), to afford 72.4 mg (55% yield) of 2x and 40.2 mg (31% yield) of 2x-II. [00249] Data for 2x: yellow solid; R/= 0.61 (hexanes/EtOAc 1: 1 (v/v)). NMR Spectroscopy: 1H NMR (600 MHz, CDC13, 23 C, delta): 7.94-7.98 (m, 4H), 7.91 (s, 1H), 7.66- 7.71 (m, 2H), 7.54-7.58 (m, 4H), 6.82 (s, 1H), 3.50 (s, 3H). 13C NMR (125 MHz, CDC13, 23 C, delta): 164.8, 154.7, 152.3, 139.6, 134.3, 129.1, 128.9, 120.6, 108.2, 56.1. Mass Spectrometry: HRMS (ESI-TOF) (m/z): calcd for C18H16C1N205S2 ([M + H]+), 439.0184, found, 439.0200. Data for 2x-II: yellow oil; R/ = 0.22 (hexanes/EtOAc 1: 1 (v/v)). NMR Spectroscopy: 1H NMR (600 MHz, CDC13, 23 C, delta): 8.29 (d, J = 5.9 Hz, 1H), 8.03 - 8.06 (m, 4H), .65-1.69 (m, 2H), 7.55 (t, J = 7.9 Hz, 4H), 6.77 (d, J = 5.9 Hz, 1H), 3.46 (s, 3H). 13C NMR (125 MHz, CDC13, 23 C, delta): 165.9, 155.0, 151.5, 139.9, 134.2, 129.5, 128.8, 119.1, 107.2, 56.2. Mass Spectrometry: HRMS (ESI-TOF) (m/z): calcd for C18H16C1N205S2 ([M + H]+), 439.0184, found, 439.0184. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
75% | With [Ag(2,2'-bipyridine)2](ClO4); C20H28N4O2Pd(2+)*2CF3O3S(1-); In acetonitrile; at 23℃; for 24h;Inert atmosphere; Sealed tube; | Under N2 atmosphere, an oven-dried 4 mL vial was charged <strong>[49562-28-9]Fenofibrate</strong> (isopropyl 2-(4-(4-chlorobenzoyl)phenoxy)-2-methylpropanoate) (108.2 mg, 0.300 mmol, 1.00 equiv), palladium complex 1 (11.4 mg, 15.0 muiotaetaomicron, 5.00 mol%), Ag(bipy)2C104 (16.0 mg, 30.0 muetaiotaomicron, 10.0 mol%), and NFBS (0.189 g, 0.600 mmol, 2.00 equiv). Acetonitrile (0.75 mL, c = 0.40 M) was added and the reaction mixture was stirred in a sealed vial at 23 C for 24 h. Subsequently, triethylamine (30.5 mg, 42.0 mu, 0.300 mmol, 1.00 equiv) was added and the reaction mixture was concentrated in vacuo. The residue was purified by chromatography on silica gel, eluting with hexanes/EtOAc (19: 1 to 5.7: 1 (v/v) with 1% triethylamine), to afford 148.4 mg of the title compound as a colorless solid (75% yield). [00258] R/= 0.57 (hexanes/EtOAc 7:3 (v/v)). NMR Spectroscopy: 1H NMR (600 MHz, CDC13, 23 C, delta): 8.01-8.04 (m, 4H), 7.86 (dd, J = 8.8, 2.3 Hz, 1H), 7.68-7.70 (m, 2H), 7.64-7.68 (m, 2H), 7.56 (d, J = 2.3 Hz, 1H), 7.53-7.56 (m, 4H), 7.43-7.46 (m, 2H), 6.70 (d, J = 8.8 Hz, 1H), 5.07 (sep, J = 6.3 Hz, 1H), 1.34 (s, 6H), 1.25 (d, J = 6.5 Hz, 6H). 13C NMR (125 MHz, CDCI3, 23 C, delta): 192.8, 172.6, 158.0, 140.4, 138.9, 136.0, 135.7, 133.8, 133.1, 131.3, 129.8, 129.0, 129.0, 128.8, 124.4, 115.9, 80.5, 69.5, 24.3, 21.7. Mass Spectrometry: HRMS (ESI-TOF) (m/z): calcd for C32H34C1N208S2 ([M + NH4]+), 673.144, found, 673.1455. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With [Ag(2,2'-bipyridine)2](ClO4); C20H28N4O2Pd(2+)*2CF3O3S(1-); In acetonitrile; at 23℃; for 24h;Inert atmosphere; Sealed tube; | Under N2 atmosphere, an oven-dried 4 mL vial was charged with l-chloro-3- fluoro-2-methoxybenzene (48.2 mg, 38.9 mu, 0.300 mmol, 1.00 equiv), palladium complex 1 (11.4 mg, 15.0 muetaiotaomicron, 5.00 mol%), Ag(bipy)2C104 (16.0 mg, 30.0 muetaiotaomicron, 10.0 mol%), and NFBS (0.189 g, 0.600 mmol, 2.00 equiv). Acetonitrile (0.75 mL, c = 0.40 M) was added and the reaction mixture was stirred in a sealed vial at 23 C for 24 h. Subsequently, triethylamine (30.5 mg, 42.0 mu, 0.300 mmol, 1.00 equiv) was added and the reaction mixture was concentrated in vacuo. The residue was purified by chromatography on silica gel, eluting with hexanes/EtOAc (19: 1 to 4: 1 (v/v) with 1% triethylamine), to afford 106.7 mg of a mixture of the title compound and its two constitutional isomers (78% yield). Purification for characterization was accomplished by preparative TLC. [00221] Data for 2k: colorless solid; R/ = 0.59 (hexanes/EtOAc 7:3 (v/v)). NMR Spectroscopy: 1H NMR (600 MHz, CDC13, 23 C, delta): 7.93-7.97 (m, 4H), 7.70-7.74 (m, 2H), 7.57-7.61 (m, 4H), 6.83 (t, J = 2.1 Hz, 1H), 6.72 (dd, J = 10.9, 2.6 Hz, 1H), 4.04 (d, J = 2.3 Hz, 3H). 13C NMR (125 MHz, CDC13, 23 C, delta): 155.1 (d, J = 251.3 Hz), 146.4 (d, J = 12.5 Hz), 139.1, 134.5, 129.4, 129.1 (d, J = 3.8 Hz), 128.8 (d, J = 1.1 Hz), 128.7, 128.4 (d, J = 5.5 Hz), 119.4 (d, J =20 Hz), 61.7 (d, J = 6.3 Hz). 19F NMR (375 MHz, CDC13, 23 C, delta): -129.0 (d, J = 9.8 Hz). Mass Spectrometry: HRMS (ESI-TOF) (m/z): calcd for [M + NH4]+, 473.0402, found, 473.0415. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With [Ag(2,2'-bipyridine)2](ClO4); C20H28N4O2Pd(2+)*2CF3O3S(1-); In acetonitrile; at 23℃; for 24h;Inert atmosphere; Sealed tube; | Under N2 atmosphere, an oven-dried 4 mL vial was charged with 2-fluoro-5- bromotoluene (56.7 mg, 38.3 mu, 0.300 mmol, 1.00 equiv), palladium complex 1 (11.4 mg, 15.0 muetaiotaomicron, 5.00 mol ), Ag(bipy)2C104 (16.0 mg, 30.0 muetaiotaomicron, 10.0 mol ), and NFBS (0.189 g, 0.600 mmol, 2.00 equiv). Acetonitrile (0.75 mL, c = 0.40 M) was added and the reaction mixture was stirred in a sealed vial at 23 C for 24 h. Subsequently, triethylamine (30.5 mg, 42.0 mu, 0.300 mmol, 1.00 equiv) was added and the reaction mixture was concentrated in vacuo. The residue was purified by chromatography on silica gel, eluting with hexanes/EtOAc (19: 1 to 4: 1 with 1% triethylamine), to afford 71.0 mg of the mixture of the title compounds as a yellow solid (63% yield). [00232] The products could not readily be separated by silica gel chromatography or preparative TLC, so they were characterized as a mixture. Compounds 2p-2p-IV were assigned through a combination of 1-D TOCSY and NOESY experiments (see page S92- S93). Data for 2p and 2p-II and 2p-III: [00233] R/= 0.57 (hexanes/EtOAc 7:3 (v/v)). NMR Spectroscopy: 1H NMR (600 MHz, CDC13, 23 C, delta): 8.07 (d, J = 8.2 Hz, 1.3H), 8.00 (d, J = 8.2 Hz, 4H), 7.96 (d, J = 8.2 Hz, 0.4H), 7.91 (d, J = 8.2 Hz, 0.6H), 7.72-7.68 (m, 2.9H), 7.66-7.62 (m, 0.3H), 7.59-7.54 (m, 5.7H), 7.53-7.49 (m, 0.7H), 7.46-7.42 (m, 1.5H), 7.31-7.27 (m, 0.2H), 7.25-7.22 (m, 0.2H), 7.01 (dd, J = 8.7, 8.7 Hz, 0.45H), 6.87 (dd, J = 9.6, 9.6 Hz, 0.2H), 6.81 (d, J = 9.6 Hz, 1H), 5.01 (s, 0.3H), 2.30 (s, 3H), 2.21 (s, 0.2H), 1.84 (s, 1.0H). 13C NMR (125 MHz, CDC13, 23 C, delta): Peaks are not listed because the mixture of four compounds, as well as splitting of aryl carbons by 19F, precluded assignment. See S91 for spectrum. Mass Spectrometry: HRMS (ESI-TOF) (m/z): calcd for Ci9H15BrNNa04S2 ([M + Na]+), 505.9504, found, 505.9502. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
79% | A: Fromferrocene: Synthesis according to the general procedurementioned above. The product is obtained with a purity >95%,containing traces of ferrocene and difluoroferrocene as indicated by1H NMR. If necessary these can be removed by HPLC.HPLC: CH3CN/H2O (60/40; isocratic). Orange solid (490 mg,2.4 mmol, 42%);B: From <strong>[1273-73-0]bromoferrocene</strong>:Under a positive pressure of argon, freshly sublimated mono<strong>[1273-73-0]bromoferrocene</strong>(300 mg, 1.14 mmol) was dissolved in dry tetrahydrofuran(20 ml) and the resulting yellow solution was cooledto 78 C. Over a period of 5 min n-butyllithium in n-hexane(0.5 ml, 1.25 mmol, 2.5 M) was added, ensuring that the temperaturedoes not exceed 70 C. After stirring for 2 h at 5 C, thesuspension of NFSI (4.3 g, 14 mmol) in diethylether (50 ml) wasadded at once. Subsequently, the reaction mixture was directlysubjected to water-cooled column (20 mm ) containing neutralalumina (Activity III). The column was washed with hexanes untilthe eluate was colorless. The organic solvents were removed underreduced pressure and the product was obtained as an orange solid.HPLC: CH3CN/H2O (60/40; isocratic). Orange solid (204 mg,1.0 mmol, 79%);1H NMR (CDCl3): δ 4.30 (dt, JHH, HF 3.0, 2.0 Hz, 2H, CpH), 4.26(s, 5H, CpH), 3.79 (td, JHH, HF 2.1, 1.3 Hz, 2H, CpH). 13C NMR(CDCl3): δ 135.8 (d, 1JCF 268 Hz, C1), 69.4 (s, C10-50), 61.2 (d,3JCF 3.8 Hz, C3,4), 56.2 (d, 2JCF 15.2 Hz, C2,5). 19F{1H} NMR(CDCl3): δ 189 (s). IR (solid): cm1 3098 (w), 1467 n(C-Caromatic,vs); 1239 n(CeF, m), 1103 (m), 803 (vs), 632 (m). MS (EI): m/z 204[M], 128 [Cp2], 121 [CpFe]; calcd for C10H9FFe 204. Anal. Calcdfor C10H9FFe: C, 58.87; H, 4.45. Found: C, 58.65; H, 4.24. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
10% | 1,10-Dibromoferrocene [23] (300 mg, 0.87 mmol) was dried for3hat 2*102 mbar in a Schlenk flask. Afterwards, itwas dissolved indry diethylether (2 ml) forming a clear yellow solution. In a separateSchlenk flask diethylether (4 ml) was cooled to 78 C and tertbutyllithiumin n-hexane (2.3 ml, 3.66 mmol,1.6M) was added. Thedissolved 1,10<strong>[1293-65-8]dibromoferrocene</strong> was added dropwise to the tertbutyllithiumsolution over a period of 5 min. The resulting mixturewas stirred at 78 C for 1 h. In an additional Schlenk flask NFSI(1.15 g, 3.66 mmol), which had been dried for 3 h in vacuo, wasdissolved in tetrahydrofurane (6 ml). The NFSI solutionwas added tothe reaction mixture within 2 min. Directly after the addition thesolution was quenched with NaBH4 and 20 ml 0.1 M Ca(OH)2.Pentane (50 ml)was added and the two-phase systemwas stirred for1 h. The organic phase was separated and washed 3 times withwater. All solvents were carefully removed in vacuo. The crudeproduct was filtered through alumina (Activity III, diameter 2 cm,length 25 cm) with pentane as mobile phase. After evaporation ofthe solvent, the crude product was purified by HPLC (CH3CN/H2O(70:30); isocratic). The HPLC fractions were extracted with pentane(4 20 ml). The organic phase was dried with MgSO4 and carefullyevaporated in vacuo (the product is volatile). The product was obtainedas a yellow solid.HPLC: CH3CN/H2O (70:30; isocratic). Yellow solid (20 mg,0.09 mmol, 10%);1H NMR (CDCl3): delta 4.39 (app. q, JHH, HF 2.2 Hz, 4H, CpH),3.91e3.89 (app. m, 4H, CpH). 13C NMR (CDCl3): delta 135.9 (d,1JCF 269 Hz, C1,10), 62.5 (d, 3JCF 3.8 Hz, C3,30,4,40), 57.5 (d,2JCF 15.1 Hz, C2,20,5,50). 19F{1H} NMR (CDCl3): delta 189 (s). IR (solid): cm1 3108 (w), 1463 n(C-Caromatic, vs); 1242 n(CeF, m), 1020 (m),803 (vs), 634 (m). MS (EI): m/z 222 [M], 139 [M CpF], 128[Cp2]; calcd for C10H8F2Fe 222.Anal. Calcd for C10H8F2Fe: C, 54.10;H, 3.63. Found: C, 53.33; H, 3.70. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
46% | 1,10-Dibromoferrocene [23] (1.8 g, 5.2 mmol) was dried for 3 h at2 * 102 mbar. Subsequently it was dissolved in dry tetrahydrofuran(20 ml) and cooled to 78 C, causing a clear orange solution. Nbutyllithiumin n-hexane (3.7 ml, 5.6 mmol, 1.6 M) was addedslowly over 15 min. The resulting suspension was stirred for anadditional 30 min. In a second Schlenk flask, a suspension of NFSI(1.81 g, 5.8 mmol, dried for 3 h in vacuo) in diethylether (20 ml) wasprepared. After 30 min the reaction mixture was transferred intothe NFSI solution via cannula. Directly after the addition the solutionwasquenched with NaBH4 and 50 ml of 0.1MCa(OH)2, and theresulting slurry was diluted with hexane (100 ml). The two phasesystem was stirred for 1 h, the organic phase was separated andwashed three times with water. After evaporation of the solvent invacuo, the resulting brown oil was dissolved again in 50 ml ofhexane and the organic phasewas extracted thrice with 0.2MFeCl3solution and subsequently 3 times with water. The organic phasewas filtered through alumina (Activity III, diameter 2 cm, length25 cm) and dried with MgSO4. After the solvents were evaporatedthe crude product was purified by HPLC (isocratic CH3CN/H2O(70:30); isocratic). The HPLC fractions were extracted with hexane(4 20 ml). The organic phase was dried with MgSO4 and evaporatedin vacuo, leaving the product as a browneorange oil.HPLC: CH3CN/H2O (70:30; isocratic). Browneorange oil (674 mg,2.40 mmol, 46%);1H NMR (CDCl3): delta 4.51 (app. s, 2H, CpH, H2?,5?), 4.33 (app. s, 2H,CpH,H2,5), 4.21 (app. s, 2H, CpH,H3?,4?), 3.88 (app. s, 2H, CpH,H3,4). 13CNMR (CDCl3): delta 135.6 (d, 1JCF 270 Hz, C1), 78.1 (s, C1?), 71.6 (s, C2?,5?),68.6 (s, C3?,4?), 64.0 (d, 3JCF 3.8 Hz, C3,4), 58.7 (d, 2JCF 15.0 Hz, C2,5).19F{1H} NMR (CDCl3): delta 189 (s). IR (ATR): cm-1 3110 (w), 1471 n(CCaromatic,vs); 1242 n(CeF, m),1152 (m), 807 (vs), 657 (m).MS(EI): m/z282 [M], 128 [Cp2]; calcd for C10H8FBrFe 282. Anal. Calcd forC10H8FBrFe: C, 42.45; H, 2.85. Found: C, 42.26; H, 2.86. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
20% | General procedure: Under a positive pressure of argon, the respective metallocene(1 equiv.) and potassium tert-butoxide (0.125 equivalents) weredissolved in dry tetrahydrofuran (1 mmol in 10 ml). The solution ofthe metallocene was cooled to 78 C and the solution of tertbutyllithiumin n-heptane (1.6 M, 2 equivs.) was added slowly,ensuring that the temperature did not exceed 70 C. Stirring wascontinued for 60 min at 78 C. After that, the suspension wastransferred into a solution of NFSI (2.5 equivs.) in dry diethylether(7 ml per 1 mmol) at 20 C. Then, the reaction mixture wasdirectly subjected to a water-cooled column containing neutralalumina gel (activity III, diameter 2 cm, length 25 cm). The columnwas eluted with hexanes until the eluent was colorless (for 1) or approx. four times (for 6), in order to remove excess NFSI and otherpolar byproducts. The solvent was removed in vacuo. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
91% | With copper(l) iodide; 1,10-Phenanthroline; In 1,2-dichloro-ethane; at 130℃; for 8h;Inert atmosphere; | General procedure: The specific preparation process: To a magnetic stirrer with 10mLA round bottom flask with a beaker was charged with acetonitrile (2 mL) as a solvent,4-methylphenylacetic acid (0.46 g, 1 mmol),N-fluorodibenzenesulfonimide (0.097 g, 1.2 mmol),Copper iodide (0.026 ml, 0.3 mmol) and1,10-o-phenanthroline (0.026 ml, 0.3 mmol),After mixing,Put it in a 80 C oil bath and continue stirring.TLC detection of substrate disappeared,The reaction is over. The reaction was poured into saturated aqueous sodium chloride (5 mL)Extract with dichloromethane (3 x 6 mL), combine the organic phases, dry over anhydrous magnesium sulfate,After depressurization, the organic solvent was distilled off under reduced pressure,The liquid mixture was obtained and finally subjected to silica gel column chromatography(Eluent V petroleum ether: V ethyl acetate = 10: 1) to give 0.41 g of a light yellow solid which was confirmed as compound (1) by NMR after MS,Based on 4-methylphenylacetic acid, the yield was calculated to be 90%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
351 mg; 573 mg | Step a: To a solution of NHMDS (1 M in THF, 8.68 mL, 8.68 mmol) was added a solution of tert-butyl 1-oxo-8-azaspiro[4.Sjdecane-8-carboxylate (2.0 g, 7.89 mmol) in THF (5 mL) at -78 C. After stirring for 30 mm at this temperature, a solution of Nfluorobenzenesulfonamide (2.49 g, 7.89 mmol) in THF (10 mL) was added. After stirring for 3 h at -78 C, the mixture was diluted with sat. aq. NaHCO3 (100 mL) and extracted with DCM (3 x 100 mL). The combined organic phases were washed with brine, dried over Na2504, filtered, and concentrated under reduced pressure. The resulting residue was purified by silica chromatography (0 to 25% gradient of EtOAc/heptane) to give racemic tert-butyl 2-fluoro- 1 -oxo8-azaspiro[4.Sjdecane-8-carboxylate (351 mg, 1.29 mmol), MS m/z 272.1 (M+H), and tert-butyl 2,2-difluoro- 1 -oxo-8-azaspiro[4.Sjdecane-8-carboxylate which coeluted with starting material. The combined difluoro ketone containing fractions were purified by silica chromatography (0 to 5%gradient of MeOH/DCM) to give tert-butyl 2,2-difluoro-1-oxo-8-azaspiro[4.5jdecane-8- carboxylate (573 mg, 1.98 mmol). MS m/z 290.1 (M+H). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
62% | With copper(l) chloride; In acetonitrile; at 70℃; for 1h;Schlenk technique; Inert atmosphere; | General procedure: An oven-dried, 5 mL Schlenk flask equipped with a stir bar was place under an atmosphere of N2. CuCl (2.45 mg, 0.025 mmol%, 5 mol%) and dissolved in 0.5 mL fresh distilled CH3CN. 2,2,6,6-Tetramethyl piperidine oxonium tetrafluoroborate (TEMPO+BF4-, 122 mg, 0.5 mmol) and hexamethyldisilane (150 mg, 154 muL, 0.75 mmol%, 1.5 equiv) were added to the above solution. N-Fluorobenzenesulfonimide (157 mg, 0.5 mmol) was dissolved in 0.5 mL fresh distilled CH3CN and added to the flask via a syringe at room temperature under nitrogen atmosphere. The resulting mixture was heated to 70 C on a preheated oil spot, and the reaction progress was monitored by TLC analysis. After completion of the reaction, the mixture was cooled to 0C, and quenched with 2 mL of ice-cold sat. NaHCO3 (aq). The remaining material was extracted three times with ethyl acetate (10 mL) and the organic layer was dried with Na2SO4, and filtrated. Evaporation of theorganic solvent and the resulting mixture was purified by column chromatography on silica gel (hexane-AcOEt 30:1 to 5:1) to afford 2,2,6,6-tetramethyl piperidine N-oxy radical (67 mg, 86 % yield) and bisbenzolsulfonimid (148 mg, quantative yield). Analytical data for bisbenzolsulfonimid NMR (400 MHz, CDCl3): delta 8.00 (d, J = 6.4, 4H), 7.75 (t, J = 6.4, 2H), 7.60 (d, J = 6.4, 4H); 13C NMR (100 MHz, CDCl3) delta 135.8, 134.5, 129.7, 129.4; HRMS (ESI), calculated for C12H11NNaO4S2 ([M+Na]+): 320.0027, found: 320.0029; TLC Rf =0.18 (EtOAc/hexane, 1/5). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
86%; 100% | With 1,1,1,2,2,2-hexamethyldisilane; copper(l) chloride; In acetonitrile; at 70℃; for 1h;Schlenk technique; Inert atmosphere; | An oven-dried, 5 mL Schlenk flask equipped with a stir bar was place under an atmosphere of N2. CuCl (2.45 mg, 0.025 mmol%, 5 mol%) and dissolved in 0.5 mL fresh distilled CH3CN. 2,2,6,6-Tetramethyl piperidine oxonium tetrafluoroborate (TEMPO+BF4-, 122 mg, 0.5 mmol) and hexamethyldisilane (150 mg, 154 muL, 0.75 mmol%, 1.5 equiv) were added to the above solution. N-Fluorobenzenesulfonimide (157 mg, 0.5 mmol) was dissolved in 0.5 mL fresh distilled CH3CN and added to the flask via a syringe at room temperature under nitrogen atmosphere. The resulting mixture was heated to 70 C on a preheated oil spot, and the reaction progress was monitored by TLC analysis. After completion of the reaction, the mixture was cooled to 0C, and quenched with 2 mL of ice-cold sat. NaHCO3 (aq). The remaining material was extracted three times with ethyl acetate (10 mL) and the organic layer was dried with Na2SO4, and filtrated. Evaporation of theorganic solvent and the resulting mixture was purified by column chromatography on silica gel (hexane-AcOEt 30:1 to 5:1) to afford 2,2,6,6-tetramethyl piperidine N-oxy radical (67 mg, 86 % yield) and bisbenzolsulfonimid (148 mg, quantative yield). Analytical data for bisbenzolsulfonimid NMR (400 MHz, CDCl3): delta 8.00 (d, J = 6.4, 4H), 7.75 (t, J = 6.4, 2H), 7.60 (d, J = 6.4, 4H); 13C NMR (100 MHz, CDCl3) delta 135.8, 134.5, 129.7, 129.4; HRMS (ESI), calculated for C12H11NNaO4S2 ([M+Na]+): 320.0027, found: 320.0029; TLC Rf =0.18 (EtOAc/hexane, 1/5). |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
25% | In acetonitrile; at 80℃; for 1h;Sealed tube; | General procedure: Procedure A: To a 10-mL reaction tube was sequentially added sulfide 1 (0.5 mmol), dry acetonitrile (1 mL), and N-fluorobis(benzenesulfonyl)imide (189 mg, 0.6 mmol). The system was quickly sealed with a Teflon cap and immersed into an 80C oil-bath. After stirring for 1 h, dichloromethane (5 mL) was added, and the solution was transferred to a 25-mL flask. The solvent was removed under reduced pressure. The residue was purified by column chromatography with a mixture of PE and EA as eluent to afford the desired imidation product 2, of which the yield was calculated based on the sulfide. Procedure B: To a 10-mL reaction tube was sequentially added sulfide 1 (0.5mmol), dry acetonitrile (1mL), and N-fluorobis(benzenesulfonyl)imide (79 mg, 0.25 mmol). The same procedure as described above afforded the desired product 2, of which the yield was calculated based on NFSI. Caution: The reaction scale and amount of sulfides, NFSI, or acetonitrile in Procedure A and Procedure B should be adjusted according to the footnotes in Table 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
77% | With copper(l) iodide; sodium hydrogencarbonate In 1,2-dichloro-ethane at 60℃; for 8h; | |
23% | In acetonitrile at 80℃; for 1h; Sealed tube; regiospecific reaction; | 26 4.4. Procedure for the sulfur-directed C(sp3)-H imidation General procedure: Procedure A: To a 10-mL reaction tube was sequentially added sulfide 1 (0.5 mmol), dry acetonitrile (1 mL), and N-fluorobis(benzenesulfonyl)imide (189 mg, 0.6 mmol). The system was quickly sealed with a Teflon cap and immersed into an 80°C oil-bath. After stirring for 1 h, dichloromethane (5 mL) was added, and the solution was transferred to a 25-mL flask. The solvent was removed under reduced pressure. The residue was purified by column chromatography with a mixture of PE and EA as eluent to afford the desired imidation product 2, of which the yield was calculated based on the sulfide. Procedure B: To a 10-mL reaction tube was sequentially added sulfide 1 (0.5mmol), dry acetonitrile (1mL), and N-fluorobis(benzenesulfonyl)imide (79 mg, 0.25 mmol). The same procedure as described above afforded the desired product 2, of which the yield was calculated based on NFSI. Caution: The reaction scale and amount of sulfides, NFSI, or acetonitrile in Procedure A and Procedure B should be adjusted according to the footnotes in Table 2. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
54% | With sodium hydrogencarbonate; In acetonitrile; at 70℃; for 12h; | Bromobenzimidazole 1e (59.1 mg, 0.3 mmol), NaHCO3 (12.6 mg, 50 mol%) and NFSI (142 mg, 1.5 equiv.) Were added to 2.0 mL of acetonitrile and the reaction was stopped at 70 C. for 12 h. Chromatography (silica gel column; eluent: petroleum ether / ethyl acetate = 25/2) gave sulfonylated 5-bromobenzimidazole 2e. The product was a white solid in 54% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
67% | With sodium hydrogencarbonate; In acetonitrile; at 70℃; for 12h; | 5 g of methoxybenzimidazole (44.5 mg, 0.3 mmol), NaHCO3 (12.6 mg, 50 mol%), NFSI (142 mg, 1.5 equiv.) Were added to 2.0 mL of acetonitrile and the reaction was stopped for 12 h at 70 C , Column chromatography (silica gel column; eluent: petroleum ether / ethyl acetate = 25/2) to give 2 g of sulfonylated <strong>[4887-80-3]5-methoxybenzimidazole</strong>. The product was a white solid in 67% yield |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
80% | With sodium hydrogencarbonate; In acetonitrile; at 70℃; for 12h; | Add 5,6-dimethylbenzimidazole (44mg, 0.3mmol), NaHCO3 (12.6mg, 50mol)%, NFSI (142mg, 1.5equiv.) To 2.0mL of acetonitrile and stop the reaction at 70 for 12h The reaction and column chromatography (silica gel column; eluent: petroleum ether / ethyl acetate = 25/2) gave sulfonylated 5,6-dimethylbenzimidazole 2h.The product is a white solid in 80% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With sodium hydrogencarbonate; In acetonitrile; at 70℃; for 12h; | 5-carboxylate benzimidazole 1i (53 mg, 0.3 mmol), NaHCO3 (12.6 mg, 50 mol%), NFSI (142mg, 1.5equiv.), Added 2.0mL of acetonitrile, the reaction was stopped after 12h at 70 , column chromatography (using silica gel Column eluent: petroleum ether / ethyl acetate = 25/2) to give sulfonylated methyl 5-carboxybenzoimidazole 2i and methyl 6-carboxylate Benzimidazole 2i, is obtained. The product was a white solid with a total yield of 81%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
81% | With sodium hydrogencarbonate; In acetonitrile; at 70℃; for 12h; | Benzotriazole 1n (36 mg, 0.3 mmol), NaHCO3 (12.6 mg, 50 mol%), NFSI (142 mg, 1.5equiv.) Was added to 2.0mL of acetonitrile, the reaction was stopped at 70 for 12h, the column chromatography (using silica gel column Agent: petroleum ether / ethyl acetate = 25/2) to give sulfonylated benzotriazole 2n. The product was a yellow solid in 81% yield. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With Bathocuproine; cesium fluoride; copper(I) bromide; In 1,2-dichloro-ethane; at 70℃; for 12h;Inert atmosphere; Schlenk technique; Sealed tube; | General procedure: Diphenylacetylene (36 mg, 0.20 mmol), NFSI (95 mg, 0.30 mmol,1.5 equiv), bathocuproine (8.7 mg, 24 μmol, 12 mol%), CuBr (2.9 mg, 20 μmol, 10mol%) and CsF (30 mg, 0.20 mmol, 1.0 equiv) were added to a Schlenk tubecontaining a magnetic stirring bar in open air. The tube was evacuated and refilledwith N2 gas following the usual Schlenk technique. Anhydrous 1,2-dichloroethane(2.0 mL, 0.10 M) was added into the tube and the reaction tube was capped with a J.Young O-ring tap. The reaction mixture was stirred and heated at 70 C for 12 h.The mixture was then cooled to room temperature. The crude mixture was filteredthrough a pad of silica gel topped with Na2SO4 in a short column and concentrated invacuo. 2-Fluorobiphenyl (17.2 mg, 0.10 mmol) was added into the crude as aninternal standard and the 19F NMR yield was determined. Purification by flashchromatography on silica gel (hexane/EtOAc = 7:1) followed by concentration invacuo provided 2a in 62% (53.3 mg, 0.124 mmol) yield as white crystals. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
With trifluorormethanesulfonic acid; trifluoroacetic acid; at 80℃; for 24h;Sealed tube; | General procedure: In a 35 mL pressure-resistant sealed tube, add chlorobenzene (2.5 mmol, 281 mg),NFSI (0.5 mmol, 157.5 mg),TfOH (0.75 mmol, 66 muL),TFA (0.5mL), stirred,The reaction was carried out at 60 C for 24 hours. After the reaction, the reaction mixture was cooled to room temperature, the solvent was distilled off under reduced pressure, and the residue was separated by silica gel column chromatography to obtain the target compound 1:Compound 1 was a white solid, 199.2 mg, yield 79%. |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
96 % ee | With iron(II) triflate; trimethylsilylazide; C58H62N2O3 In chloroform at 20℃; for 48h; Schlenk technique; Inert atmosphere; Overall yield = 95 percent; Overall yield = 76.7 mg; stereoselective reaction; |
Yield | Reaction Conditions | Operation in experiment |
---|---|---|
97% | Stage #1: 3-bromostyrene; N-fluorobis(benzenesulfon)imide With (1R,2R)-(-)-N,N'-bis(3,5-di-tert-butylsalicydene)-1,2-cyclohexanediaminocobalt(II) In 1,4-dioxane for 0.166667h; Inert atmosphere; Glovebox; Stage #2: With 1,1,3,3-Tetramethyldisiloxane In 1,4-dioxane at 20℃; for 3h; Inert atmosphere; Sealed tube; regioselective reaction; | |
49% | With cobalt(salen); 9-bora-bicyclo[3.3.1]nonane In tetrahydrofuran; ethyl acetate at 60℃; for 10h; Schlenk technique; Inert atmosphere; |
Tags: 133745-75-2 synthesis path| 133745-75-2 SDS| 133745-75-2 COA| 133745-75-2 purity| 133745-75-2 application| 133745-75-2 NMR| 133745-75-2 COA| 133745-75-2 structure
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H420 | Harms public health and the environment by destroying ozone in the upper atmosphere |
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