Directing-Group-Based Strategy Enabling Intermolecular Heck-Type Reaction of Cycloketone Oxime Esters and Unactivated Alkenes

Org Lett. 2020 May 1;22(9):3524-3530. doi: 10.1021/acs.orglett.0c00963. Epub 2020 Apr 15.

Abstract

A new type of coupling between unactivated olefins and nonstabilized alkyl radicals was achieved, which enabled the first intermolecular Heck-type reaction of cycloketone oxime esters and unactivated alkenes. This directing-group-based strategy was compatible with various unactivated alkenes and cyclobutanone-, cyclopentanone-, and cyclohexanone-derived oxime esters. Density functional theory calculations showed that both excellent regioselectivities and good diastereoselectivities could be ascribed to the 2-butanol-assisted concerted H-OBz elimination of the conformationally strained metallacyclic transition state.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkenes*
  • Catalysis
  • Esters*
  • Oximes

Substances

  • Alkenes
  • Esters
  • Oximes