[H-].[Na+].[CH3:3][O:4][CH2:5][O:6][C:7]1[CH:8]=[C:9]([CH:19]=[C:20]([O:22][CH2:23][O:24][CH3:25])[CH:21]=1)[CH2:10][O:11][Si:12]([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13].CN([CH2:29][CH2:30]N(C)C)C.[Li][CH2:35][CH2:36][CH2:37][CH3:38].[Br-].[CH2:40]1[CH2:44]OC[CH2:41]1>[Cu]I>[CH3:3][O:4][CH2:5][O:6][C:7]1[CH:8]=[C:9]([CH:19]=[C:20]([O:22][CH2:23][O:24][CH3:25])[C:21]=1[CH2:44]/[CH:40]=[CH:41]/[C:30]1[CH:29]=[CH:38][CH:37]=[CH:36][CH:35]=1)[CH2:10][O:11][Si:12]([C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:14])[CH3:13]To a suspension of NaH (60%, 18 g, 0.45 mol) in THF (2 L) were added (3,5-bis-methoxymethoxy-benzyloxy)-tert-butyl-dimethyl-silane (220c) (100 g, 0.3 mol) and TMEDA (81.6 g, 0.6 mol) in one portion. The mixture was stirred at 0° C. for 1 hr. n-BuLi (2.5 M in hexane, 180 mL, 0.45 mol) was added drop wise to the mixture at −20° C. and the solution was stirred for 1 hr. CuI (114 g, 0.6 mol) was added in one portion and the reaction was stirred at −20° C. for another 1 hr. Then the mixture was added drop wise cinamy bromide (65 g, 0.3 mol) at −20° C. After stirring for another 30 min, TLC (EtOAc/petroleum ether=1/10) showed that the reaction was complete. The reaction mixture was quenched with H2O (500 mL). The organic layer was separated and the aqueous layer was extracted with EtOAc (2×500 mL). The organic layers were combined, washed with brine (1 L), dried over Na2SO4 and concentrated to give a dark oil. The crude oil was purified by column chromatography (EtOAc/petroleum ether=1/10) to give the title compound (55 g, 34%) as a yellow liquid. 1H NMR (400 MHz, CDCl3): δ 7.16-7.41 (m, 5H), 6.82 (s, 2H), 6.47 (m, 2H), 5.22 (s, 4H), 4.71 (s, 2H), 3.62 (d, 2H), 3.45 (s, 6H), 0.94 (s, 9H), 0.12 (s, 6H).
Wird geladen…