Work

Aldehyde–Olefin Couplings Via Sulfoxylate-Mediated Oxidative Generation of Ketyl Radical Anions

Year: 2024

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide Ketyl radicals are valuable reactive intermediates because they allow carbonyl chemistry to be extended beyond traditional electrophilic reactivity through simple single-electron reduction to a nucleophilic radical. However, this pathway is challenging due to the large negative reduction potentials of carbonyls, thus requiring highly reducing conditions. Herein, we describe the development of an alternative strategy to access ketyl radicals from aldehydes, which avoids the reduction pathway by instead proceeding via single-electron oxidation and desulfination of α-hydroxy sulfinates. These redox-active aldehyde adducts are generated in situ through the addition of sulfoxylate (SO 2 2– ) to aldehydes and possess low oxidation potentials, thereby facilitating ketyl radical formation and circumventing the need for strongly reducing conditions. We demonstrate the application of this sulfoxylate-mediated ketyl radical formation in ketyl–olefin coupling reactions.

Source: Journal of the American Chemical Society

DOI: 10.1021/jacs.4c10093

Authors: Zhihang Li, Joseph A. Tate, Adam Noble

Institutions: University of Bristol, Syngenta (United Kingdom)

Language: English

Topic: Radical Photochemical Reactions

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $4,500

Funders: Engineering and Physical Sciences Research Council, EPSRC Centre for Doctoral Training in Technology Enhanced Chemical Synthesis