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Published January 16, 2013 | Published + Accepted Version + Supplemental Material
Journal Article Open

Nickel-Catalyzed Carbon−Carbon Bond-Forming Reactions of Unactivated Tertiary Alkyl Halides: Suzuki Arylations

Abstract

The first Suzuki cross-couplings of unactivated tertiary alkyl electrophiles are described. The method employs a readily accessible catalyst (NiBr_2·diglyme/4,4′-di-tert-butyl-2,2′-bipyridine, both commercially available) and represents the initial example of the use of a group 10 catalyst to cross-couple unactivated tertiary electrophiles to form C–C bonds. This approach to the synthesis of all-carbon quaternary carbon centers does not suffer from isomerization of the alkyl group, in contrast with the umpolung strategy for this bond construction (cross-coupling of a tertiary alkylmetal with an aryl electrophile). Preliminary mechanistic studies are consistent with the generation of a radical intermediate along the reaction pathway.

Additional Information

© 2013 American Chemical Society. Received: November 29, 2012; published: January 2, 2013. Support was provided by the National Institutes of Health (National Institute of General Medical Sciences, R01-GM62871) and Merck Research Laboratories (summer fellowship for S.L.Z.). We thank Dr. Alexander S. Dudnik for preliminary observations.

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Published - ja311669p.pdf

Accepted Version - nihms-432697.pdf

Supplemental Material - ja311669p_si_001.pdf

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Created:
August 19, 2023
Modified:
October 23, 2023