Dramatic Enhancement of Reactivity of Organosilicon Compounds Induced by Complexation of Bis(allyl)silanes with Fluoride Ion
作者:Atsushi Shibato、Yoshifumi Itagaki、Eiji Tayama、Yasutoshi Hokke、Naoki Asao、Keiji Maruoka
DOI:10.1016/s0040-4020(00)00458-0
日期:2000.7
New type of fluoride ion catalyzed allylation agent (1a, 1b), allenylation agent (9, 10), and alkynylation agent (17) can be successfully utilized for various carbonyl substrates. The rate acceleration is ascribable to the shift of equilibrium to the chelate complexes with Bu4NF by the favorable chelation of bis(silyl) compounds toward the fluoride ion. The 19F NMR spectrum (ethyl trifluoroacetate
氟化物离子催化的烯丙基化剂(新类型1A,1B),allenylation剂(9,10),和炔基化剂(17)可以被成功地用于各种羰基的底物。通过双(甲硅烷基)化合物向氟离子的有利螯合,速率加速归因于平衡转移至具有Bu 4 NF的螯合物的螯合物。1a和Bu 4 NF的混合物在CDCl 3中的19 F NMR光谱(三氟乙酸乙酯为外标)在δ处显示两个峰-81.75和-77.67(积分比〜9:1)。大信号对应于Bu 4 NF的原始峰,小信号可能归因于1a和Bu 4 NF之间的螯合物[ B ] 。检查了双(巴甲基二甲基甲硅烷基)甲烷(7)与苯甲醛的氟离子介导的反应,并且选择性地获得了唯一的γ-加合物8。