Journal article

Publication year: 2014

Pages: 10669-10673

Journal: The Journal of Organic Chemistry

Volume number: 79

Issue number: 21

Open access status: Bronze

DOI Link: https://doi.org/10.1021/jo502021x

Publisher: American Chemical Society

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.

Harvard Citation style: Barabash, A., Butova, E., Kanyuk, I., Schreiner, P. and Fokin, A. (2014) Beyond the Corey Reaction II: Dimethylenation of Sterically Congested Ketones, The Journal of Organic Chemistry, 79(21), pp. 10669-10673. https://doi.org/10.1021/jo502021x

APA Citation style: Barabash, A., Butova, E., Kanyuk, I., Schreiner, P., & Fokin, A. (2014). Beyond the Corey Reaction II: Dimethylenation of Sterically Congested Ketones. The Journal of Organic Chemistry. 79(21), 10669-10673. https://doi.org/10.1021/jo502021x