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

Chuan Zhu, Ze-Yao Liu, Luning Tang, Heng Zhang, Yu-Feng Zhang, Patrick J. Walsh () and Chao Feng ()
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Chuan Zhu: Nanjing Tech University
Ze-Yao Liu: Nanjing Tech University
Luning Tang: Nanjing Tech University
Heng Zhang: Nanjing Tech University
Yu-Feng Zhang: Nanjing Tech University
Patrick J. Walsh: University of Pennsylvania
Chao Feng: Nanjing Tech University

Nature Communications, 2020, vol. 11, issue 1, 1-10

Abstract: 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 mechanistic and radical trapping studies with primary alkyl bromides suggest a unique mode of tertiary C-radical generation through chain-walking followed by Ni–C bond homolysis. This strategy is complementary to the existing coupling protocols with tert-alkyl organometallic or -alkyl halide reagents, and it enables the expedient formation of quaternary centers from easily available starting materials.

Date: 2020
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DOI: 10.1038/s41467-020-18658-4

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