Engaging Tertiary Benzylic Radicals in Metallaphotoredox Catalysis: A Modular Approach to Access Diaryl Quaternary Centers

S Samantha L. Goldschmid (Department of Chemistry Columbia University New York NY 10027 USA) H Holly L. Hutchinson (Department of Chemistry Columbia University New York NY 10027 USA) T Trevor C. Sherwood (Global Discovery Chemistry) C Candice L. Joe (Chemical Process Development, Bristol Myers Squibb, 1 Squibb Drive, New Brunswick, New Jersey 08903, United States) E Eric R. Welin (Global Discovery Chemistry, Bristol Myers Squibb, 10300 Campus Point Drive, Suite 100, San Diego, California 92121, United States) T Tomislav Rovis (Department of Chemistry)

Abstract

Abstract Herein we report the decarboxylative cross‐coupling of tertiary benzylic carboxylic acids and aryl bromides to furnish all‐carbon diaryl quaternary centers. For the first time, tertiary benzylic radicals are introduced as viable participants in metallaphotoredox‐catalyzed cross‐couplings by suppressing undesired benzylic radical dimerization via fast radical trapping with Cu. We demonstrate the functionalization of feedstock carboxylic acids as well as late‐stage functionalization of carboxylic acid‐containing drugs.

Article Details

Volume / Issue Vol. 65, Issue 4
Published January 22, 2026
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (6)

S

Samantha L. Goldschmid

Department of Chemistry Columbia University New York NY 10027 USA

H

Holly L. Hutchinson

Department of Chemistry Columbia University New York NY 10027 USA

T

Trevor C. Sherwood

Global Discovery Chemistry

C

Candice L. Joe

Chemical Process Development, Bristol Myers Squibb, 1 Squibb Drive, New Brunswick, New Jersey 08903, United States

E

Eric R. Welin

Global Discovery Chemistry, Bristol Myers Squibb, 10300 Campus Point Drive, Suite 100, San Diego, California 92121, United States

T

Tomislav Rovis

Department of Chemistry