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33846275060
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To the aqueous solution (2.9 mL) containing olefin 212 (41 mg) were added the solutions of aqueous 50% N-methylmorpholine-N- oxide (4.4 mL) and aqueous 4% OsO4 (0.53 mL, and the resultant mixture was stirred at 40 °C for 130 min. After being concentrated in vacuo, the reaction solution was added dropwise to a mixture (60 mL) of acetone and methanol (4:2 v/v, The white precipitates were collected by filtration, dissolved in water (100 mL, and chromatographed on a Lobar column (Rp 18, size B) with an elution of water (150 mL) and a second gradient elution from water to 20% aqueous MeOH (500 mL for each) to give 3 (33.3 mg, 64, mp 190 °C; [α]D25, 61.7 (c, 0.125 in H 2O, 1H NMR (500 MHz, D2O, 35 °C, MeCN) δ, 4.86 (d, 3J(H,H, 2.3 Hz, 7H, H1, 3.97 (dd, 3J(H,H, 2.3, 3.3 Hz, 7H, H2, 3.85 (dd, 3JH,H, 3
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+].
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28
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0345686435
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29
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33846282013
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Synthesis of 5: an olefin 414 (25 mg, N-methylmorpholine-N-oxide (23.4 mg, and aqueous 0.1 M OsO 4 (40 μL) solution was added to a mixed solvent composed of water (0.5 mL) and MeCN (1 mL, The resultant mixture was stirred at room temperature for 6 days. After the addition of a saturated aqueous solution of Na 2SO3 (2 mL, the reaction mixture was extracted three times with AcOEt. The extracts were combined, washed with 1 M HCl and then water, and dried over Na2SO4. Evaporation of the solvents afforded crude 5 (28.4 mg) which was purified by preparative TLC on silica gel (eluted with of AcOEt) to give pure 5 (22.7 mg, 80, 1H NMR (500 MHz, CDCl3, 35 °C, TMS) δ, 7,49 and 7.37 (m, 5H, C6H5, 5.57 (s, 1H, benzylic H, 4.77 (s, 1H, H1, 4.29 (dd, 3J(H,H, 3.7, 9.2 Hz, 1H, H6, 4.08-4.05 m, 2H, H2 and H3
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