Highly Selective Allylborations of Aldehydes Using alpha,alpha-Disubstituted Allylic Pinacol Boronic Esters

Matthew J. Hesse, Stephanie Essafi, Charlotte G. Watson, Jeremy N. Harvey, David Hirst, Christine L. Willis, Varinder K. Aggarwal*

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

34 Citations (Scopus)
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Abstract

alpha,alpha-Disubstituted allylic pinacol boronic esters undergo highly selective allylborations of aldehydes to give tetrasubstituted homoallylic alcohols with exceptional levels of anti-Z-selectivity (>20:1). The scope of the reaction includes both acyclic and cyclic allylic boronic esters which lead to acyclic and exocyclic tetrasubstituted homoallylic alcohols. The use of beta-borylated allylic boronic esters gave fully substituted alkenes bearing a boronic ester which underwent further cross-coupling enabling a highly modular and stereo-selective approach to the synthesis of diaryl tetrasubstituted alkenes. Computational analysis revealed the origin of the remarkable selectivity observed.

Original languageEnglish
Pages (from-to)6145-6149
Number of pages5
JournalAngewandte Chemie - International Edition
Volume53
Issue number24
Early online date5 May 2014
DOIs
Publication statusPublished - 5 May 2014

Structured keywords

  • BCS and TECS CDTs

Keywords

  • alkenes
  • allylation
  • asymmetric synthesis
  • C-C coupling
  • synthetic methods
  • ORIENTED ORGANIC-SYNTHESIS
  • OXIDATIVE HECK ARYLATION
  • STEREOSELECTIVE-SYNTHESIS
  • TETRASUBSTITUTED ALKENES
  • ENANTIOSELECTIVE SYNTHESIS
  • HOMOALLYLIC ALCOHOLS
  • DIASTEREOSELECTIVE SYNTHESIS
  • SECONDARY ALCOHOLS
  • REACTION SEQUENCE
  • INTERNAL ALKYNES

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