Catalytic, Stereoselective Dihalogenation of Alkenes: Challenges and Opportunities

Alexander J. Cresswell, Stanley T.C. Eey, Scott E. Denmark

Research output: Contribution to journalReview article

Abstract

Although recent years have witnessed significant advances in the development of catalytic, enantioselective halofunctionalizations of alkenes, the related dihalogenation of olefins to afford enantioenriched vicinal dihalide products remains comparatively underdeveloped. However, the growing number of complex natural products bearing halogen atoms at stereogenic centers has underscored this critical gap in the synthetic chemist's arsenal. This Review highlights the selectivity challenges inherent in the design of enantioselective dihalogenation processes, and formulates a mechanism-based classification of alkene dihalogenations, including those that may circumvent the "classical" haliranium (or alkene-dihalogen π-complex) intermediates. A variety of metal and main group halide reagents that have been used for the dichlorination or dibromination of alkenes are discussed, and the proposed mechanisms of these transformations are critically evaluated.

Original languageEnglish (US)
Pages (from-to)15642-15682
Number of pages41
JournalAngewandte Chemie - International Edition
Volume54
Issue number52
DOIs
StatePublished - Dec 21 2015

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Keywords

  • alkenes
  • catalysis
  • dihalogenation
  • enantioselective synthesis
  • reaction mechanisms

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

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