Compound 11
(8S,9S,10R,13S,14S,17R)-17-(3-((S)-1,3-dimethyl-2-oxoindolin-3-yl)propanoyl)-17-hydroxy-10,13-dimethyl-1,6,7,8,9,10,12,13,14,15,16,17-dodecahydro-3H-cyclopenta[a]phenanthrene-3,11(2H)-dione
From: Photochemical generation of radicals from alkyl electrophiles using a nucleophilic organic catalyst
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Compound data: 1H NMR
Compound data: 13C NMR
Synthetic procedure: See article for the definitive version of this procedure and for full experimental details.
Compound 11 was synthesized according to the general procedure outlined for compound 8a using cortisone mesylate 9 (219.3 mg, 0.5 mmol, 1.0 equiv.) and N-methyl-N-phenylmethacrylamide (131.4 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 NMR spectroscopic analysis of the crude reaction mixture by comparison of the resonances at δ 3.17 (minor diastereomer) and δ 3.14 (major diastereomer). Chromatography on silica gel (gradient from 40% to 100% AcOEt in hexanes as eluent): 142 mg major diastereomer as an off-white solid and 62 mg minor diastereomer (isolated as 2.2:1 dr mixture favoring the minor diastereomer, off-white solid), 79% combined yield. 1H NMR for major diastereomer (500 MHz, CDCl3) δ 7.31-7.28 (m, 1H), 7.16 (d, J = 6.6 Hz, 1H), 7.10-7.07 (m, 1H), 6.87 (d, J = 7.8 Hz, 1H), 5.73 (s, 1H), 3.19 (s, 3H), 2.96-2.91 (m, 1H), 2.88 (d, J = 12.1 Hz, 1H), 2.78-2.66 (m, 2H), 2.51-2.38 (m, 3H), 2.32-2.27 (m, 2H), 2.21-2.09 (m, 2H), 2.01 (d, J = 12.5 Hz, 1H), 1.99-1.87 (m, 5H), 1.67-1.57 (m, 2H) 1.39 (s, 3H), 1.38 (s, 3H), 1.36-1.25 (m, 2H), 0.49 (s, 3H). 13C NMR (126 MHz, CDCl3) δ 211.1, 209.8, 199.8, 180.6, 168.8, 142.7, 134.2, 128.1, 124.5, 122.9, 122.7, 108.3, 89.1, 62.6, 50.5, 50.3, 49.7, 47.0, 38.2, 36.6, 34.7, 33.7, 33.5, 33.2, 32.5, 32.3, 32.3, 26.3, 23.3, 22.6, 17.2, 15.8. HRMS (ESI pos): calculated for C32H40NO5+ (M+H+): 518.2901, found 518.2904. Stereochemistry of the major diastereomer was determined by synthesis of the brominated derivative 11-Br, which was purified (the major diastereomer was isolated) and analyzed by x-ray diffraction.
