Regio- and Stereospecific 1,3-Allyl Group Transfer Triggered by a Copper-Catalyzed Borylation/ortho-Cyanation Cascade

Angew Chem Int Ed Engl. 2016 Jan 4;55(1):345-9. doi: 10.1002/anie.201508294. Epub 2015 Oct 28.

Abstract

A copper-catalyzed borylation/ortho-cyanation/allyl group transfer cascade was developed. Initiated by an unconventional copper-catalyzed electrophilic dearomatization, this process features regio- and stereospecific 1,3-transposition of the allyl fragment enabled by an aromatization-driven Cope rearrangement. This method provides an effective means for the construction of adjacent tertiary and quaternary stereocenters with excellent diastereocontrol.

Keywords: CC activation; copper; cyanation; dearomatization; sigmatropic rearrangement.

Publication types

  • Research Support, N.I.H., Extramural

MeSH terms

  • Boronic Acids / chemical synthesis*
  • Boronic Acids / chemistry
  • Catalysis
  • Copper / chemistry*
  • Molecular Structure
  • Nitriles / chemical synthesis*
  • Nitriles / chemistry
  • Organometallic Compounds / chemistry*
  • Stereoisomerism

Substances

  • Boronic Acids
  • Nitriles
  • Organometallic Compounds
  • Copper