Work

Nickel Catalysis via S H 2 Homolytic Substitution: The Double Decarboxylative Cross-Coupling of Aliphatic Acids

Year: 2022

Type: article

Abstract: Cross-coupling platforms are traditionally built around a sequence of closed-shell steps, such as oxidative addition, transmetalation, and reductive elimination. Herein, we describe a dual photo/nickel catalytic manifold that performs cross-coupling via a complementary sequence involving free radical generation, radical sorting via selective binding to a Ni(II) center, and bimolecular homolytic substitution (S H 2) at a high-valent nickel–alkyl complex. This catalytic manifold enables the hitherto elusive cross-coupling of diverse aliphatic carboxylic acids to generate valuable C(sp 3 )–C(sp 3 )-products. Notably, the powerful S H 2 mechanism provides general access to sterically encumbered quaternary carbon centers, addressing a long-standing challenge in fragment coupling chemistry.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.2c08989

Authors: Artem V. Tsymbal, Lorenzo Delarue Bizzini, David W. C. MacMillan

Institution: Princeton University

Language: English

Topic: Catalytic Cross-Coupling Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green