Work

Homologation of Alkenyl Carbonyls via a Cyclopropanation/Light‐Mediated Selective C−C Cleavage Strategy

Year: 2024

Type: article

Abstract: We report herein our studies on the direct photoactivation of carbonyl cyclopropanes to give biradical intermediates, leading to selective cleavage of the more substituted carbon‐carbon bond. Depending on the substrate structure, extended alkenes were isolated or directly reacted in a photo‐Nazarov process to give bicyclic products. Based on these results, a unified reductive ring‐opening reaction was developed by using diphenyl disulfide as a hydrogen atom transfer (HAT) reagent. By performing a sequential cyclopropanation/selective ring opening reaction, we achieved a CH2 insertion into the α,β bond of both acyclic and cyclic unsaturated carbonyl compounds. Our protocol provides a further tool for the modification of the carbon framework of organic compounds, complementing the recent progress in “skeletal editing”.

Source: Angewandte Chemie

DOI: 10.1002/ange.202417719

Authors: Tin V. T. Nguyen, Duncan K. Brownsey, André Bossonnet, Matthew D. Wodrich, Jerome Waser

Institution: École Polytechnique Fédérale de Lausanne

Language: English

Topic: Cyclopropane Reaction Mechanisms

Subfield: Organic Chemistry

Field: Chemistry

Domain: Physical Sciences

Open Access status: hybrid

Estimated APC paid: $5,250

Funders: National Science Foundation, École Polytechnique Fédérale de Lausanne, Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung