Work

Native functionality in triple catalytic cross-coupling: sp 3 C–H bonds as latent nucleophiles

Year: 2016

Type: article

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 α-amino and α-oxy sp(3) C-H bonds in both cyclic and acyclic systems.

Source: Science

DOI: 10.1126/science.aaf6635

Authors: Megan H. Shaw, Valerie W. Shurtleff, Jack A. Terrett, James D. Cuthbertson, David W. C. MacMillan

Institution: Princeton University

Language: English

Topic: Catalytic C–H Functionalization Methods

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: National Institutes of Health, National Institute of General Medical Sciences

Awards: Photoredox Catalysis Applications in Organometallics and Chemical Biology, G1588828791, G30908861