Stereospecific ring contraction of bromocycloheptenes through dyotropic rearrangements via nonclassical carbocation-anion pairs

Shermin S. Goh, Pier Alexandre Champagne, Sureshbabu Guduguntla, Takashi Kikuchi, Makoto Fujita, K. N. Houk, Ben L. Feringa

Research output: Contribution to journalArticlepeer-review

5 Scopus citations

Abstract

Experimental and theoretical evidence is reported for a rare type I dyotropic rearrangement involving a [1,2]-alkene shift, leading to the regio- and stereospecific ring contraction of bromocycloheptenes. This reaction occurs under mild conditions, with or without a Lewis acid catalyst. DFT calculations show that the reaction proceeds through a nonclassical carbocation-anion pair, which is crucial for the low activation barrier and enantiospecificity. The chiral cyclopropylcarbinyl cation may be a transition state or an intermediate, depending on the reaction conditions.

Original languageEnglish (US)
Pages (from-to)4986-4990
Number of pages5
JournalJournal of the American Chemical Society
Volume140
Issue number15
DOIs
StatePublished - Apr 18 2018
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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