Work

Excited-State Palladium-Catalyzed Radical Allylic Alkylation: Rapid Access to C2-Allyl Carbohydrates

Year: 2025

Type: article

Abstract: Glycomimetics has emerged as a promising strategy to mimic the biological activities of carbohydrates while enhancing drug-like properties. Yet, their efficient synthesis and modifications remain a major challenge. Herein, we report an excited-state Pd-catalyzed, rapid synthesis of C2-allylated carbohydrates, useful synthons for preparing glycomimetics, from readily available α-bromosugars. The transformation features a high level of atom economy, broad functional group tolerance, and suitability for late-stage modification of complex molecules. Preliminary experimental and computational studies suggest a radical mechanism involving excited Pd species, 1,2-radical migration (RaM), and kinetic-controlled β-H elimination processes. We anticipate that our findings will broaden the reaction profile of excited-state Pd catalysis and enable rapid access to valuable glycomimetics.

Source: ACS Catalysis

DOI: 10.1021/acscatal.5c00555

Authors: Wang Yao, Jaclyn N. Mauro, Yue Fu, Hang Chen, Peng Liu, Ming-Yu Ngai

Institutions: State University of New York, Stony Brook University, University of Pittsburgh, Purdue University West Lafayette

Language: English

Topic: Radical Photochemical Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: green

Funders: National Institutes of Health, National Institute of General Medical Sciences, Office of Advanced Cyberinfrastructure