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Updated: Apr 23, 2026

A Microwave-Assisted Direct Heteroarylation of Ketones Using Transition Metal Catalysis
Published on: February 16, 2020
Beyond the corey reaction II: dimethylenation of sterically congested ketones
Anastasiya V Barabash1, Ekaterina D Butova, Igor M Kanyuk
1Department of Organic Chemistry, Kiev Polytechnic Institute , pr. Pobedy 37, 03056 Kiev, Ukraine.
Abstract:
Bulky methyl ketones show significantly decreased reactivities toward the Corey-Chaykovsky methylenation reagent dimethylsulfoxonium methylide (DMSM). The excess of base and temperature increase opens an alternative reaction channel that instead leads to the corresponding cyclopropyl ketones. Computations suggest that the initial reaction step involves the methylene group transfer from DMSM on the ketone enolate followed by the intramolecular cyclization. The key step is associated with a barrier of 22 ± 3 kcal mol(-1) and is driven by exothermic elimination of DMSO.
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