The mechanistic puzzle of transition-metal-catalyzed skeletal rearrangements of enynes

Chemistry. 2006 Aug 7;12(23):5916-23. doi: 10.1002/chem.200600174.

Abstract

Three pathways actually compete in metal-catalyzed cyclizations of enynes in which the metal selectively activates the alkyne: an endocyclic process and two exo-cyclizations, one proceeding by anti attack of the alkene and a second one resulting in a syn addition. Although cyclobutenes may be formed in transition-metal-catalyzed cyclization of some enynes, particularly, 1,7-enynes, these compounds are not necessarily the intermediates in the skeletal rearrangement. Cyclobutenes are formed by ring expansion of syn-cyclopropyl metal-carbenes formed in the syn pathway.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkenes / chemical synthesis*
  • Alkenes / chemistry
  • Alkynes / chemistry*
  • Catalysis
  • Cyclization
  • Molecular Conformation
  • Stereoisomerism
  • Transition Elements / chemistry*

Substances

  • Alkenes
  • Alkynes
  • Transition Elements