Studies on retro-[1,4] Brook rearrangement of 3-silyl allyloxysilanes. Observation of the formation of unusual 3,3-bissilyl enols
Studies on retro-[1,4] Brook rearrangement of 3-silyl allyloxysilanes. Observation of the formation of unusual 3,3-bissilyl enols
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3-甲硅烷基烯丙氧基硅烷的逆[1,4]布鲁克重排研究。
DOI：
10.1016/j.tet.2012.06.005
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发表时间：
2012-08-26
期刊：
影响因子：
2.1
通讯作者：
Li, Linjie
中科院分区：
文献类型：
--
作者：
Gan, Zubao;Wu, Ya;Li, Linjie
Detailed investigations of the retro-[1,4] Brook rearrangement of 3-silyl allyloxysilanes are described. Based on control experiments and NMR studies, rationalizations are proposed for the formation of 3,3-bissilyl enols, unusual compounds that are stable to acidic hydrolysis but that can be transformed into the corresponding aldehydes under basic hydrolysis conditions. These studies further show that the 3,3-bissilyl enolates can be O-alkylated by alkyl halides with complete chemoselectivity. This reaction provides a practical entry to various 3,3-bissilyl aldehydes and enol derivatives. As a demonstration of the synthetic utility of this approach, 3,3-bissilyl aldehyde was converted into bissilyl divinyl ketone, which can undergo an SiO2-promoted Nazarov reaction to give cyclic beta-silyl enone smoothly. (C) 2012 Elsevier Ltd. All rights reserved.
