N - To C -sulfonyl photoisomerisation of dihydropyridinones: A synthetic and mechanistic study

Pei Pei Yeh, James E. Taylor, Daniel G. Stark, David S.B. Daniels, Charlene Fallan, John C. Walton, Andrew D. Smith

Research output: Contribution to journalArticlepeer-review

5 Citations (Scopus)

Abstract

The scope and limitations of a photoinitiated N- to C-sulfonyl migration process within a range of dihydropyridinones is assessed. This sulfonyl transfer proceeds without erosion of either diastereo- or enantiocontrol, and is general across a range of N-sulfonyl substituents (SO2R; R = Ph, 4-MeC6H4, 4-MeOC6H4, 4-NO2C6H4, Me, Et) as well as C(3)-(aryl, heteroaryl, alkyl and alkenyl) and C(4)-(aryl and ester) substitution. Crossover reactions indicate an intermolecular step is operative within the formal migration process, although no crossover from C-sulfonyl products was observed. EPR studies indicate the intermediacy of a sulfonyl radical and a mechanism is proposed based upon these observations.

Original languageEnglish
Pages (from-to)8914-8922
Number of pages9
JournalOrganic and Biomolecular Chemistry
Volume15
Issue number42
Early online date16 Oct 2017
DOIs
Publication statusPublished - 14 Nov 2017

ASJC Scopus subject areas

  • Biochemistry
  • Physical and Theoretical Chemistry
  • Organic Chemistry

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