Photochemical Ring Expansion of Cyclic Sulfoximines with Aryl Diazoacetates and Subsequent Diastereoconvergent Oxidation
Year: 2024
Type: article
Abstract: A visible light-mediated ring expansion reaction of cyclic N-sulfenyl sulfoximines with aryl diazoacetates is presented.The protocol results in the formation of six-membered heterocycles through the formation of sulfur ylide intermediates and a subsequent [1,2]sigmatropic rearrangement.The reaction proceeds well under ambient conditions and gives the desired heterocycles in moderate to good yields with a good functional group tolerance.Subsequent oxidation of the products with m-CPBA results in significant diastereomeric enrichment of the products.Density functional theory studies indicate that the diastereoconvergent oxidation is enabled by a ring opening and recyclization, which allow the diastereomeric ratio to adjust to a value governed by the differing thermodynamic stabilities of the diastereomers.
Source: CCS Chemistry
Institutions: RWTH Aachen University, University of Jyväskylä
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: diamond
OpenAlex ID: W4404415086