* 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.
Stage #1: aniline With tert.-butylnitrite; boron trifluoride diethyl etherate In acetonitrile Cooling with ice;
Stage #2: N-[(trifluoromethyl)sulfanyl]aniline With 1-aminomorpholine; bismuth(III) chloride; 1,4-diazabicyclo [2.2.2] octane-1,4-diium-1,4-disulfinate In acetonitrile at 80 - 100℃;
1 Example 1
Air atmosphere,In the ice water bath1.8 parts by weightTert-butyl nitriteAnd 1.5 parts by weight of aniline was droppedAnd 1.8 parts by weight of boron trifluoride diethyl ether in acetonitrile,Magnetic stirrer for 2-3 minutes.then,To the reaction system0.6 part by weight of DABSO (DABCO · (SO2) 2) was added,1.0 part by weight of N-aminomorpholine,1.3 parts by weight of N-trifluoromethylthioanilineAnd 2.0 parts by weight of bismuth chloride.The temperature of the system was raised to 80-100 ,The reaction was continued for 6-12 hours,The reaction was monitored by TLC until complete reaction.The reaction solution was extracted with ethyl acetate at the time of post-Anhydrous Na2SO4 dry,The purified product aryl trifluoromethanesulfonate 2a was isolated by flash column chromatography using a decompression solvent.Isolated yield: 74%;
With toluene-4-sulfonic acid In 1,2-dichloro-ethane at 20℃;
General procedure for the synthesis of compound 3
General procedure: Sulfonyl chloride 1 (0.2 mmol) was added into a solution of Na2SO3 (2.0 equiv) and NaHCO3 (2.0 equiv) in H2O (1.0 mL). The mixture was stirred at 80°C for 4h. After evaporation of water, PhNHSCF3 2 (0.3 mmol), 4-methylbenzenesulfonic acid (0.5mmol) and DCE (2 ml) were added. The mixture was stirred at room temperature. After completion of the reaction as indicated by TLC, the reaction mixture was filtered by sand core funnel with silica gel and washed by CH2Cl2. The volatiles were removed and the residue was purified by flash column chromatography (SiO2) to provide the final products 3. S-trifluoromethyl benzenesulfonothioate (3a). 1H NMR (400 MHz, CDCl3) δ 7.60-7.63 (m, 2H), 7.72-7.76 (m, 1H), 8.01 (d, J = 7.6Hz, 2H); 13C NMR (100 MHz, CDCl3) δ 127.3 (q, J = 311.4 Hz), 127.6, 129.7, 135.2,144.6; 19F NMR (378 MHz, CDCl3) δ -38.5 (s); HRMS (EI) calcd for C7H5F3O2S2+:241.9678 (M+), found: 241.9685
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Inert atmosphere; Irradiation; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Inert atmosphere; Irradiation; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Inert atmosphere; Irradiation; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Inert atmosphere; Irradiation; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Inert atmosphere; Irradiation; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Inert atmosphere; Irradiation; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Inert atmosphere; Irradiation; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Inert atmosphere; Irradiation; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Inert atmosphere; Irradiation; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Inert atmosphere; Irradiation; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Irradiation; Inert atmosphere; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Irradiation; Inert atmosphere; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Irradiation; Inert atmosphere; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Irradiation; Inert atmosphere; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Irradiation; Inert atmosphere; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Irradiation; Inert atmosphere; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Irradiation; Inert atmosphere; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Irradiation; Inert atmosphere; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Irradiation; Inert atmosphere; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Irradiation; Inert atmosphere; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Irradiation; Inert atmosphere; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Irradiation; Inert atmosphere; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Irradiation; Inert atmosphere; Overall yield = 74%; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Irradiation; Inert atmosphere; Overall yield = 77%; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Irradiation; Inert atmosphere; Overall yield = 77%; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Irradiation; Inert atmosphere; regioselective reaction;
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Irradiation; Inert atmosphere; regioselective reaction;
(8R,9S,13S,14S)-3-ethynyl-13-methyl-7,8,9,11,12,13,15,16-octahydro-6H-cyclopenta[a]phenanthren-17(14H)-one (8R,9S,13S,14S)-3-ethynyl-13-methyl-7,8,9,11,12,13,15,16-octahydro-6H-cyclopenta[a]p[ No CAS ]
C27H27F3O3S2[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
65%
With tris(2,2'-bipyridyl)ruthenium dichloride; [bis(trifluoromethanesulfonyl)imidate](triphenylphosphine)gold(I) In 1,4-dioxane at 20℃; for 6h; Irradiation; Inert atmosphere; regioselective reaction;
(4-(4-iodophenoxy)butan-2-yl)(trifluoromethyl)sulfane[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
74%
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere; regioselective reaction;
1 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
4-(3-((trifluoromethyl)thio)butoxy)benzaldehyde[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
63%
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere; regioselective reaction;
2 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
1-(4-(3-((trifluoromethyl)thio)butoxy)phenyl)ethanone[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
65%
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere; regioselective reaction;
3 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
ethyl 4-(3-((trifluoromethyl)thio)butoxy)benzoate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
74%
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere; regioselective reaction;
4 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
5-((trifluoromethyl)thio)hexyl 4-chlorobenzoate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
58%
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere; regioselective reaction;
5 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
5-((trifluoromethyl)thio)hexyl 4-bromobenzoate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
72%
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere; regioselective reaction;
6 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
5-((trifluoromethyl)thio)hexyl furan-2-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
57%
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere; regioselective reaction;
11 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
5-((trifluoromethyl)thio)hexyl thiophene-2-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
59%
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere; regioselective reaction;
12 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
(13S)-13,17-dimethyl-17-((trifluoromethyl)thio)-7,8,9,11,12,13,14,15,16,17-decahydro-6H-cyclopenta[a]phenanthren-3-yl acetate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
71%
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere; regioselective reaction;
19 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
5-((trifluoromethyl)thio)hexyl 4-methoxybenzoate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
91%
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere; regioselective reaction;
7 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
5-((trifluoromethyl)thio)hexyl 4-fluorobenzoate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
68%
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere; regioselective reaction;
8 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
4-((trifluoromethyl)thio)pentyl 4-(trifluoromethyl)benzoate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
73%
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere; regioselective reaction;
9 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
4-((trifluoromethyl)thio)pentyl 4-(methylsulfonyl)benzoate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
70%
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere; regioselective reaction;
10 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
4-((trifluoromethyl)thio)pentyl 4-methylbenzenesulfonate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
73%
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere; regioselective reaction;
13 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
4-((trifluoromethyl)thio)pentyl 4-chlorobenzenesulfonate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
91%
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere; regioselective reaction;
14 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
3-methyl-3-((trifluoromethyl)thio)butyl 1-methyl-1H-pyrrole-2-carboxylate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
75%
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere; regioselective reaction;
15 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
3-methyl-3-((trifluoromethyl)thio)butyl 4-cyanobenzoate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
52%
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere; regioselective reaction;
16 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere; regioselective reaction;
17 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
3-methyl-3-((trifluoromethyl)thio)butyl 2-(1-(phenylsulfonyl)-1H-indol-3-yl)acetate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
51%
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere; regioselective reaction;
18 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
3-methyl-1-tosyl-4-(((trifluoromethyl)thio)methyl)pyrrolidine[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
65%
With tert.-butylhydroperoxide; 2-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)-2,2-diphenylacetic acid potassium salt; phenylsilane; cobalt(II) diacetate tetrahydrate In ethanol at 28℃; for 6h; Schlenk technique; Inert atmosphere;
21 1.4 General procedure for hydrogen-trifluoromethylthiolation of olefins
General procedure: Co(OAc)2·4H2O (7.5 mg, 6.0 mol%), ligand L1 (15.0 mg, 6.0 mol%) were placed into an oven-dried Schlenk tube that was equipped with a stirring bar under an argon atmosphere. 2.5 mL of ethanol was added into the Schlenk tube. The solution was stirred at 28 °C for 15 min. Then, tBuOOH (27.5 μL, 0.55 M in decene, 30.0 mol%) was added under an argon atmosphere, The solution was stirred at 28 °C for another 15 min. At last, olefins (0.5 mmol), PhSO2SCF3 (242 mg, 1.00 mmol, 2.00 equiv), PhSiH3 (87 mg, 0.80 mmol, 1.6 equiv) were added. The reaction was stirred at 28 °C for 6 h. 10 mL of distilled water and 40 mL of Et2O were added and the organic phase was separated and washed with 25 mL of saturated brines twice. The separated organic phase was dried over anhydrous Na2SO4, and concentrated in vacuo. The product was purified by flash chromatography on silica gel.
(3S,4aS,5aR,6aS,6bS,9R,9aR,11aS,11bR)-3-(allylsulfonyl)-9a,11b-dimethyl-9-((R)-6-methylheptan-2-yl)hexadecahydrocyclopenta[1,2]phenanthro[8a,9-b]oxirene[ No CAS ]
(4aS,5aR,6aS,6bS,9R,9aR,11aS,11bR)-9a,11b-dimethyl-9-((R)-6-methylheptan-2-yl)-3-((trifluoromethyl)thio)hexadecahydrocyclopenta[1,2]phenanthro[8a,9-b]oxirene[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
81%
With 2,2'-azobis(isobutyronitrile) In chloroform at 85℃; for 48h; Inert atmosphere; Schlenk technique; diastereoselective reaction;
2-(4-((3-(4-methoxy-3-(pentyloxy)phenyl)-2-oxotetrahydropyrimidin-1(2H)-yl)methyl)-1H-pyrrolo[2,3-b]pyridin-1-yl)-N,N-dimethylacetamide[ No CAS ]
2-(4-((3-(4-methoxy-3-(pentyloxy)phenyl)-2-oxotetrahydropyrimidin-1(2H)-yl)methyl)-3-((trifluoromethyl)thio)-1H-pyrrolo[2,3-b]pyridin-1-yl)-N,N-dimethylacetamide[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
With tetra-(n-butyl)ammonium iodide In acetonitrile at 20℃; Irradiation;
22
Following a modified protocol reported by Li. et al. (Chem. Sci., 2018, 9, 5781): A 20 -mL vial is charged with 2-(4-((3-(4-methoxy-3-(pentyloxy)phenyl)-2- oxotetrahydropyrimidin-1(2H)-yl)methyl)-1H-pyrrolo[2,3-b]pyridin-1-yl)-N,N- dimethylacetamide (150 mg, 0.30 mmol) and S-(trifluoromethyl) benzenesulfonothioate (143 mg, 0.59 mmol). The vial is evacuated and purged with argon three times. A solution of tetrabutylammonium iodide (22 mg, 0.06 mmol) in degassed, anhydrous acetonitrile (3 mL) is added to the vial. The reaction is stirred at room temperature overnight while being irradiated by a household compact fluorescent lightbulb (CFL). The reaction is diluted with ethyl acetate, then filtered through CELITE. The filter cake is thoroughly washed with ethyl acetate. The filtered solution is concentrated in vacuo. Purification by column chromatography over reversed-phase C18 silica gel afforded 2-(4-((3-(4-methoxy-3- (pentyloxy)phenyl)-2-oxotetrahydropyrimidin-1(2H)-yl)methyl)-3-((trifluoromethyl)thio)- 1H-pyrrolo[2,3-b]pyridin-1-yl)-N,N-dimethylacetamide.