Compound 11-Br

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Compound data: 1H NMR

Compound data: 13C NMR

Compound data: Crystallographic data

Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.

Compound 11-Br was synthesized according to the general procedure outlined for compound 8a using cortisone mesylate (219.3 mg, 0.5 mmol, 1.0 equiv.) and N-(4-bromophenyl)-N-methylmethacrylamide (190.6 mg, 0.75 mmol, 1.5 equiv.). 20 mol % catalyst was used: 1c (31.0 mg, 0.10 mmol, 0.2 equiv.). The diastereomeric ratio was determined by ¹H spectroscopic analysis of the crude reaction mixture by comparison of the resonances at δ 3.12 (minor diastereomer) and δ 3.09 (major diastereomer). Chromatography on silica gel (gradient from 40% to 100% AcOEt in hexanes as eluent): 98 mg major diastereomer (33% yield; only collected pure fractions of major diastereomer) as a white solid. Recrystallization from heptane and ethyl acetate provided a crystal, which was analyzed by x-ray diffraction.¹H NMR for major diastereomer (500 MHz, CDCl₃) δ 7.41 (dd, J = 8.3, 1.9 Hz, 1H), 7.27 (d, J = 2.1 Hz, 1H), 6.74 (d, J = 8.3 Hz, 1H), 5.72 (s, 1H), 3.71 (bs, 1H), 3.15 (s, 3H), 3.03-2.97 (m, 1H), 2.89 (d, J = 12.5 Hz, 1H), 2.77-2.69 (m, 2H), 2.51-2.38 (m, 3H), 2.31-2.27 (m, 2H), 2.17-2.06 (m, 2H), 2.02 (d, J = 12.5 Hz, 1H), 1.99-1.86 (m, 5H), 1.67-1.59 (m, 2H), 1.39 (s, 3H), 1.37 (s, 3H), 1.35-1.25 (m, 2H), 0.51 (s, 3H). ¹³C NMR for major diastereomer (126 MHz, CDCl₃) δ 211.1, 210.0, 200.0, 180.4, 168.9, 142.1, 136.8, 131.3, 126.3, 125.0, 116.0, 110.1, 89.5, 63.0, 50.8, 50.7, 50.1, 47.5, 38.5, 37.0, 35.1, 34.1, 33.4, 32.9, 32.7, 32.6, 31.3, 26.7, 23.6, 22.8, 17.6, 16.2.IR (thin film) ν 3440, 2938, 1703, 1668, 1607, 1488, 1346, 1270, 1131, 735 cm^-1. HRMS (ESI pos): calculated for C₃₂H₃₈⁷⁹BrNNaO₅⁺ (M+Na⁺): 618.1826, found 618.1831.