Migratory functionalization of unactivated alkyl bromides for construction of all-carbon quaternary centers via transposed tert-C-radicals.

ABSTRACT: Despite remarkable recent advances in transition-metal-catalyzed C(sp³)-C cross-coupling reactions, there remain challenging bond formations. One class of such reactions include the formation of tertiary-C(sp³)-C bonds, presumably due to unfavorable steric interactions and competing isomerizations of tertiary alkyl metal intermediates. Reported herein is a Ni-catalyzed migratory 3,3-difluoroallylation of unactivated alkyl bromides at remote tertiary centers. This approach enables the facile construction of otherwise difficult to prepare all-carbon quaternary centers. Key to the success of this transformation is an unusual remote functionalization via chain walking to the most sterically hindered tertiary C(sp³) center of the substrate. Preliminary mechanist

SUBMITTER: Zhu C 

PROVIDER: S-EPMC7519689 | biostudies-literature | 2020 Sep

REPOSITORIES: biostudies-literature