Brook rearrangements have been employed extensively in our and other Laboratories in conjunction with a multicomponent coupling tactic we now term Anion Relay Chemistry (ARC). Although negative charge interchange via migration of a silyl group is now well-known, Brook rearrangements via single-electron transfer (SET) have not been extensively explored. We have designed and achieved an oxidative [1,2]-Brook rearrangement involving visible-light-induced SET exploiting the oxidation of hypervalent silicon species. The resulting alkyl radical was found to engage both in conjugate additions to achieve formal alkylation and in radical coupling reactions to achieve arylation.

Oxidative [1,2]-Brook rearrangements exploiting single-electron transfer: Photoredox-catalyzed alkylations and arylations

255th National Meeting (2018)

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