Stereocontrolled synthesis of 1,5-stereogenic centers through three-carbon homologation of boronic esters

Phillip J. Unsworth, Daniele Leonori, Varinder K. Aggarwal*

*Corresponding author for this work

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

13 Citations (Scopus)

Abstract

Allylic pinacol boronic esters are stable toward 1,3-borotropic rearrangement. We developed a PdII-mediated isomerization process that gives di- or trisubstituted allylic boronic esters with high E selectivity. The combination of this method with lithiation-borylation enables the synthesis of carbon chains that bear 1,5-stereogenic centers. The utility of this method has been demonstrated in a formal synthesis of (+)-jasplakinolide. Three more: The 3C homologation of chiral pinacol boronic esters gives di- or trisubstituted allylic boronic esters with high yield and E selectivities. The combination of this method with lithiation-borylation enables the synthesis of alkyl chains that bear 1,5-stereogenic centers. The utility of the process was demonstrated in a formal synthesis of (+)-jasplakinolide.

Original languageEnglish
Pages (from-to)9846-9850
Number of pages5
JournalAngewandte Chemie - International Edition
Volume53
Issue number37
DOIs
Publication statusPublished - 8 Sep 2014

Structured keywords

  • BCS and TECS CDTs

Keywords

  • 1,5-stereocenters
  • allylic boronic esters
  • asymmetric synthesis
  • lithiation-borylation
  • palladium

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