title: [1,5]-Brook rearrangement: an overlooked but valuable silyl migration to synthesize configurationally defined vinylsilane. The unique steric and electronic effects of geminal bis(silane).
abstract: An unusual [1,5]-Brook rearrangement of the lithium alkoxide of geminal bis(silyl) homoallylic alcohol is described. The unique steric and electronic effects of geminal bis(silane) were found to be crucial for promoting this long-range silyl migration, as well as for facilitating the subsequent γ/Z-selective addition of silyl allyllithium with carbonyl compounds to synthesize diverse configurationally defined Z-vinylsilanes.
authors: Key Laboratory of Drug-Targeting and Drug Delivery System of the Education Ministry, Department of Medicinal Chemistry, West China School of Pharmacy, Sichuan University, Chengdu, 610041, China. zhenleisong@scu.edu.cn.
authors: Lu
authors: L
authors: Gao
authors: Ji
authors: J
authors: Lu
authors: Zhenlei
authors: Z
authors: Song
authors: Xinglong
authors: X
authors: Lin
authors: Yongjin
authors: Y
authors: Xu
authors: Zhiping
authors: Z
authors: Yin
mesh_terms: D000438:Alcohols / Q000737:chemistry; D000447:Aldehydes / Q000737:chemistry; D004583:Electrons; D007659:Ketones / Q000737:chemistry; D012821:Silanes / Q000138:chemical synthesis / Q000737:chemistry*; D012997:Solvents / Q000737:chemistry; D013237:Stereoisomerism; D014753:Vinyl Compounds / Q000138:chemical synthesis / Q000737:chemistry*
chemical_list: D000438:Alcohols; D000447:Aldehydes; D007659:Ketones; D012821:Silanes; D012997:Solvents; D014753:Vinyl Compounds; C476909:vinylsilane