C-C Bond Activation and Demethylenation of Epoxides by Amine Radical Dications

Eric Holt; Nathaniel G Garrison; Rozhin Rowshanpour; Justin Jeeyoung Kim; Nicolas Henriquez; Winson Lam; Neil Kiame; Jack Williams; Sherrie Zhao; Travis Dudding; Thomas Lectka

doi:10.1021/acs.joc.3c00605

C-C Bond Activation and Demethylenation of Epoxides by Amine Radical Dications

J Org Chem. 2023 Jun 2;88(11):7597-7600. doi: 10.1021/acs.joc.3c00605. Epub 2023 May 9.

Authors

Eric Holt^{1

2}, Nathaniel G Garrison^{1

2}, Rozhin Rowshanpour^{1

2}, Justin Jeeyoung Kim^{1

2}, Nicolas Henriquez^{1

2}, Winson Lam^{1

2}, Neil Kiame^{1

2}, Jack Williams^{1

2}, Sherrie Zhao^{1

2}, Travis Dudding^{1

2}, Thomas Lectka^{1

2}

Affiliations

¹ Department of Chemistry, Johns Hopkins University, 3400 North Charles St., Baltimore, Maryland 21218, United States.
² Department of Chemistry, Brock University, St. Catharines, Ontario L2S3A1, Canada.

PMID: 37159569
DOI: 10.1021/acs.joc.3c00605

Abstract

In this note, we explore a unique reactivity pattern that involves a rare radical-based C-C bond scission of epoxides followed by demethylenation. The reaction is accomplished by Selecfluor and its radical dication working in tandem; a mechanism supported by experiment and DFT calculations is proposed that involves the generation and identification of a key reactive intermediate. The reaction seems to be fairly general for 1,1-disubstituted epoxides.