Work

Light‐Driven Enantioselective Carbene‐Catalyzed Radical‐Radical Coupling

Year: 2023

Type: article

Abstract: An enantioselective carbene‐catalyzed radical‐radical coupling of acyl imidazoles and racemi c Hantzsch esters is disclosed. This method involves the coupling of an N‐heterocyclic carbene‐derived ketyl radical and a secondary sp 3 ‐carbon radical and allows access to chiral α‐aryl aliphatic ketones in moderate‐to‐good yields and enantioselectivities without any competitive epimerization. The utility of this protocol is highlighted by the late‐stage functionalization of various pharmaceutical compounds and is further demonstrated by the transformation of the enantioenriched products to biologically relevant molecules. Computational investigations reveal the N‐heterocyclic carbene controls the double‐facial selectivity of the ketyl radical and the alkyl radicals, respectively.

Source: Angewandte Chemie International Edition

DOI: 10.1002/anie.202312829

Authors: Seunghwan Byun, Meemie U. Hwang, Henry R. Wise, Anna V. Bay, Paul H.‐Y. Cheong, Karl A. Scheidt

Institutions: Northwestern University, Oregon State University

Language: English

Topic: N-Heterocyclic Carbenes in Organic and Inorganic Chemistry

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: National Science Foundation, Directorate for Mathematical and Physical Sciences, National Institute of General Medical Sciences, Division of Chemistry

Awards: G4725248420, G7127280876, G749739012