Experimental

Olefin9 (59 mg, 0.21 mmol, 1 equiv.) was dissolved in a solution of 3:1 acetone:H2O (4 mL), OsO4 (218 µL, 0.02 mmol, 0.1 equiv.) and N-Methylmorpholine-N-Oxide (NMO) (32 mg, 0.27 mmol, 1.3 equiv.) were then added. The reaction mixture was stirred at room temperature for twelve hours. After this time, the reaction was quenched at room temperature by the dropwise addition of saturated aqueous NaHCO3 (25 mL). The reaction mixture was separated using saturated aqueous Na2S2O3 (10 mL) and dichloromethane (CH2Cl2) (15 mL). The aqueous layer was extracted twice with dichloromethane (10 mL, 2 twice). The combined organic layers were washed with H2O (20 mL), brine (20 mL), and dried with anhydrous MgSO4. Volitiles were removed in vacuo and the remaining material was purified by silica gel flash chromatography (1:1 ethyl acetate:hexanes) to produce a colorless solid, triol (61 mg).
Triol (45 mg, 0.145mol, 1 equiv.) was dissolved in dichloromethane (5 mL). Then, 5% aqueous NaHCO3 (2.0 mL), potassium bromide (KBr) (1.7 mg, 0.014 mmol, 0.10 equiv) and 2,2,6,6-Tetramethylpiperidine-1-oxyl (TEMPO) (2.2 mg, 0.014 mmol, .10 equiv.) were all added. The biphasic mixture was then cooled to 0 ˚C in an ice bath and stirred rapidly. Bleach (commercial bleach solution, 6% NaOCl) (0.27 mL, 0.22 mmol, 1.5 equiv.) was added dropwise to the stirring reaction mixture. The reaction mixture was stirred for 1.5 hours at 0˚C and then separated using saturated aqueous Na2S2O3 (10 mL) and dichloromethane (10 mL). The aqueous layer was extracted twice with dichloromethane (10 mL, 2 twice), and the combined organic layers were washed with brine (25 mL) and dried with anhydrous MgSO4. Volitiles were removed in vacuo and the remaining material was purified by silica gel flash chromatography (1:1 ethyl acetate:hexanes) to yield ketone 10 (37 mg, 85%) as a white foam.: TLC (EtOAc:hexanes, 1:1 v/v): Rf = 0.5; 1H NMR (600
MHz, CDCl3) δ 4.35 (d, J = 3.9 Hz, 1 H), 3.86 (bs, 1 H), 2.75 (dd, J = 17.7, 9.8 Hz, 1 H), 2.44 (d, J = 9.6 Hz, 1 H), 2.22 (d, J = 17.8 Hz, 1 H), 2.15 (bs, 1 H), 1.96 (s, 2 H), 1.73 – 1.66 (m, 4 H), 1.67 – 1.60 (m, 2 H), 1.57 – 1.41 (m, 4 H), 1.45 –1.34 (m, 2 H), 1.00 (d, J = 4.3 Hz, 3 H), 0.94 (d, J = 6.4 Hz, 3 H), 0.86 (d, J = 6.6 Hz, 6 H); 13C NMR (150 MHz, CDCl3) δ 213.9, 76.6, 73.4, 58.6, 42.4, 40.5, 38.7, 37.5, 36.1, 35.4, 31.6, 31.5, 29.0, 25.5, 24.7, 24.0, 21.5, 20.4, 14.2; IR (film) νmax 3438, 2955, 1711, 1465, 1374, 1235, 1099, 941 cm-1; HRMS (m/z): [M+Na]+ calcd. for C19H32NaO3, 331.2244; found, 331.2245.