Benzenesulfonic Acid, 4-Methyl, [[(1R)-2,2,2-Trichloro-1-phenylethoxy]carbonyl]azanyl Ester and Benzenesulfonic Acid, 4-Methyl, [[(1S)-2,2,2-Trichloro-1-phenylethoxy]carbonyl]azanyl Ester

Benzenesulfonic acid, 4-methyl, [[(1R)-2,2,2-trichloro-1-phenylethoxy]carbonyl]azanyl ester [1335126-79-8] C16H14Cl3NO5S (MW 438.70) InChI = 1S/C16H14Cl3NO5S/c1-11-7-9-13(10-8-11)26(22,23)25-20-15(21)24-14(16(17,18)19)12-5-3-2-4-6-12/h2-10,14H,1H3,(H,20,21)/t14-/m1/s1 InChIKey = MNEVHLLVXMRRPL-CQSZACIVSA-N Benzenesulfonic acid, 4-methyl, [[(1S)-2,2,2-trichloro-1-phenylethoxy]carbonyl]azanyl ester [1335126-80-1] C16H14Cl3NO5S (MW 438.70) InChI = 1S/C16H14Cl3NO5S/c1-11-7-9-13(10-8-11)26(22,23)25-20-15(21)24-14(16(17,18)19)12-5-3-2-4-6-12/h2-10,14H,1H3,(H,20,21)/t14-/m0/s1 InChIKey = MNEVHLLVXMRRPL-AWEZNQCLSA-N (chiral reagents used as metal nitrene precursors to undergo stereoselective CH and aziridinations of alkenes) Physical Data: (R)-OTs: (c 1.00, MeOH).1 mp 86–87 °C; 1H NMR (300 MHz, CDCl3); δ 8.14 (s, 1H), 7.86 (d, J = 8.3 Hz, 2H), 7.47–7.34 (m, 5H), 7.29–7.26 (m, 2H), 6.11 (s, 1H), 2.42 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 153.2, 146.4, 131.7, 130.0, 129.8, 129.68, 129.65, 129.5, 128.0, 98.4, 84.5, 21.8; IR (neat) 3490, 3188, 2956, 1766, 1652, 1597, 1483, 1383, 1237, 1190, 1182, 1088, 1036, 810, 771, 744, 724, 697 cm−1; HRMS (ESI+) calc. for C16H14NCl3O5SNa [M + Na]+: 459.95505; found: 459.95599.1 Solubility: sol aromatic hydrocarbons (toluene, benzene, chlorobenzene, trifluorotoluene), ether, chloroform, dichloromethane, ethyl and isopropyl acetate. Form Supplied in: white solid. Preparative Method: N-tosyloxy-2,2,2-trichloro-1-phenylcarbamate is readily prepared from 2,2,2-trichloro-1-phenylethanol. The corresponding hydroxycarbamate is produced using carbonyldiimidazole (CDI) and hydroxylamine, and then reacted with p-tosyl chloride under standard reaction conditions to afford the desired reagent (eq 1).1 (1) Purification: recrystallized from a mixture of chloroform/hexanes (1/1) or flash chromatography on silica gel with 20% Et2O/pentane. Handling, Storage, and Precautions: stable at rt for up to 6 months; thermogravimetry analysis showed decomposition at >180 °C.