Enantioselective preparation and chemoselective cross-coupling of 1,1-diboron compounds

Nat Chem. 2011 Sep 25;3(11):894-9. doi: 10.1038/nchem.1150.

Abstract

The simplicity, efficiency and generality of the transition-metal-catalysed Suzuki-Miyaura cross-coupling reaction has led to its application in the preparation of a wide variety of organic compounds. Cross-coupling of alkylboron derivatives, however, remains a major challenge, in particular with regard to stereochemical control. Here, we describe the preparation and reaction of highly optically enriched 1,1-diboron compounds. A catalytic asymmetric conjugate borylation of β-boronylacrylates provided geminal diboronate products that feature two distinct boronyl units, in 99% enantiomeric excess. Chemoselective cross-coupling of one-boronyl unit, a trifluoroborate salt, occurred stereospecifically via inversion of its configuration to generate enantioenriched benzylic or allylic boronates. The difficult transmetallation in the Suzuki-Miyaura catalytic reaction cycle is believed to be facilitated by a stabilization effect from the second boronyl unit, and internal coordination by the oxygen of the proximal carboxyester. We also explored subsequent functionalization of the second boronyl unit.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Boron Compounds / chemistry*
  • Boronic Acids / chemistry
  • Catalysis
  • Crystallography, X-Ray
  • Molecular Conformation
  • Stereoisomerism
  • Transition Elements / chemistry

Substances

  • Boron Compounds
  • Boronic Acids
  • Transition Elements

Associated data

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