Work

Asymmetric Desymmetrizing Sulfonylation of Diarylmethanes via Peptidyl-Cu(I)-Catalysis with Remote Stereocontrol

Year: 2026

Type: article

Abstract: An asymmetric catalytic desymmetrizing cross-coupling of diarylmethanes with organosulfinates has been developed. Permutations of proteinogenic and noncanonical amino acids allow access to guanidinylated peptide-based ligands that may be tuned for distal stereocontrol under copper catalysis. Noncovalent attractive interactions are likely significant in organizing the geometry of substrate-copper-peptide ternary complexes, modulated by countercation effects, for effective enantioselective oxidative addition; further enantioenrichment of the sulfone products occurs via secondary kinetic resolution, corroborated by mechanistic studies. The mild protocols disclosed herein expand asymmetric and site-selective catalysis mediated by peptides first to enable C-S bond-forming cross-coupling reactions with remote stereocontrol.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.5c20554

Authors: Hyun-Suk Um, Scott J. Miller

Institution: Yale University

Language: English

Topic: Sulfur-Based Synthesis Techniques

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funders: National Research Foundation of Korea, National Institutes of Health, National Institute of General Medical Sciences