Boron-Promoted Deprotonative Conjugate Addition: Geminal Diborons as Soft Pronucleophiles and Acyl Anion Equivalents

J Org Chem. 2022 Aug 5;87(15):9896-9906. doi: 10.1021/acs.joc.2c00914. Epub 2022 Jul 12.

Abstract

Conjugate addition of α-boron-stabilized carbanions is an underexplored reaction modality. Existing methods require deborylation of geminal di-/triboryl alkanes and/or the presence of additional activating groups. We report the 1,4-addition of α,α-diboryl carbanions generated via deprotonation of the corresponding geminal diborons. The methodology provided a general route to highly substituted and synthetically useful γ,γ-diboryl ketones. The development of geminal diborons as soft pronucleophiles also enabled their use as acyl anion equivalents via a one-pot tandem conjugate addition-oxidation sequence.

Publication types

  • Research Support, Non-U.S. Gov't
  • Research Support, N.I.H., Extramural

MeSH terms

  • Anions
  • Boron*
  • Ketones*
  • Oxidation-Reduction

Substances

  • Anions
  • Ketones
  • Boron