[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)

• DOI: 10.1039/c3cc45002c
• Publication Date: 2013-08-01T13:01:27Z
• Authors: Lu Gao; Ji Lu; Zhenlei Song; Xinglong Lin; Yongjin Xu; Zhiping Yin
• Keywords: Geminal; Vinylsilane; Alkoxide; Silanes

An unusual [1,5]-Brook rearrangement of the lithium alkoxide geminal bis(silyl) homoallylic alcohol is described. The unique steric and electronic effects bis(silane) were found to be crucial for promoting this long-range silyl migration, as well facilitating subsequent γ/Z-selective addition allyllithium with carbonyl compounds synthesize diverse configurationally defined Z-vinylsilanes.