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Native functionality in triple catalytic cross-coupling: sp³ C-H bonds as latent nucleophiles.

ABSTRACT: The use of sp(3) C-H bonds--which are ubiquitous in organic molecules--as latent nucleophile equivalents for transition metal-catalyzed cross-coupling reactions has the potential to substantially streamline synthetic efforts in organic chemistry while bypassing substrate activation steps. Through the combination of photoredox-mediated hydrogen atom transfer (HAT) and nickel catalysis, we have developed a highly selective and general C-H arylation protocol that activates a wide array of C-H bonds as native functional handles for cross-coupling. This mild approach takes advantage of a tunable HAT catalyst that exhibits predictable reactivity patterns based on enthalpic and bond polarity considerations to selectively functionalize ?-amino and ?-oxy sp(3) C-H bonds in both cyclic and acyclic systems.

SUBMITTER: Shaw MH

PROVIDER: S-EPMC5114852 | biostudies-literature | 2016 Jun

REPOSITORIES: biostudies-literature

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Native functionality in triple catalytic cross-coupling: sp³ C-H bonds as latent nucleophiles.

Shaw Megan H MH Shurtleff Valerie W VW Terrett Jack A JA Cuthbertson James D JD MacMillan David W C DW

Science (New York, N.Y.) 20160428 6291

The use of sp(3) C-H bonds--which are ubiquitous in organic molecules--as latent nucleophile equivalents for transition metal-catalyzed cross-coupling reactions has the potential to substantially streamline synthetic efforts in organic chemistry while bypassing substrate activation steps. Through the combination of photoredox-mediated hydrogen atom transfer (HAT) and nickel catalysis, we have developed a highly selective and general C-H arylation protocol that activates a wide array of C-H bonds ...[more]

PMID: 27127237

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