Metal-catalyzed rearrangement of homoallylic ethers to silylmethyl allylic silanes in the presence of a Di-tert-butylsilylene source.
[reaction: see text] In examining the scope of the di-tert-butylsilylene transfer to gem-disubstituted alkenes to form silacyclopropanes, we discovered an unprecedented reaction of homoallylic ethers. When silylene transfer was performed at room temperature or above, two di-tert-butylsilylene units were incorporated into the molecule, and complete rearrangement of the carbon backbone occurred. This report describes the scope of this unique reaction as well as the mechanistic studies conducted that led to a proposed mechanism.
Cleary
Pamela A
PA
Department of Chemistry, University of California, Irvine, California 92697-2025, USA.
Woerpel
K A
KA
D000475:Alkenes / Q000737:chemistry; D002384:Catalysis; D004987:Ethers / Q000737:chemistry*; D012821:Silanes / Q000138:chemical synthesis* / Q000737:chemistry
D000475:Alkenes; D004987:Ethers; D012821:Silanes