Reaction Steps
m-Chloroperoxybenzoic acid (≦77%, 273.5 mg, 1.22 mmol) is added in one portion to a solution of crude ethyl 15 (from above ˜1.22 mmol) in methylene chloride (5.0 mL) at room temperature. The reaction mixture is stirred for 1 h, diluted with methylene chloride (10 mL), and washed with a saturated aqueous solution of sodium bicarbonate (25 mL). The organic layer is dried over magnesium sulfate and evaporated under reduced pressure to give the crude product. This material is purified by flash column chromatography (eluting with ethyl acetate; Rf 0.37) to give 290.9 mg of pure ethyl 16 as a white solid. 1H NMR (CDCl3): δ 0.54 (m, 1H, c-Pr CH2 (A)), 0.93 (m, 1H, c-Pr CH2 (B)), 1.12 (m, 1H, c-Pr CH2 (A)), 1.28 (m, 1H, c-Pr CH2 (B)), 1.38 (t, J=7.0 Hz, 3H, CO2CH2CH3), 3.26 (s, 3H, S(O)CH3), 3.83 (s, 3H, OCH3), 3.92 (m, 1H, c-Pr CH), 4.40 (m, 2H, overlapping CO2CHHCH3), 7.58 (d, J=8.5 Hz, 1H, aromatic H-6), 7.87 (d, J=8.5 Hz, 1H, aromatic H-5). 13C{1H} NMR (CDCl3): δ 10.8 (br, c-Pr CH2 (A)), 13.9 (br, c-Pr CH2 (B)), 14.1 (CO2CH2CH3), 35.1 (c-Pr CH), 41.4 (S(O)—CH3), 61.1 (OCH3), 62.1 (CO2CH2CH3), 118.9 (C-3), 122.8 (CH, C-5), 123.9 (C—Br, C-7), 129.5 (C-4a), 130.0 (CH, C-6), 138.2 (C-8a), 148.3 (C—OCH3, C-8), 164.0 (CO2CH2CH3), 164.1 (br, C—S(O)—CH3, C-2), 174.6 (C═O, C-4). LCMS m/z calcd for C17H1879BrNO5S ([M]+) 427. Found 428 ([M+H]+). HRMS m/z calcd for C17H1879BrNNaO5S 449.9987 ([M+Na]+). Found 449.9977.
