Asymmetric carbon-carbon bond formation gamma to a carbonyl group: phosphine-catalyzed addition of nitromethane to allenes

J Am Chem Soc. 2009 Oct 14;131(40):14231-3. doi: 10.1021/ja9061823.

Abstract

A chiral phosphine catalyzes the addition of a carbon nucleophile to the gamma position of an electron-poor allene (amide-, ester-, or phosphonate-substituted), in preference to isomerization to a 1,3-diene, in good ee and yield. This strategy provides an attractive method for the catalytic asymmetric gamma functionalization of carbonyl (and related) compounds.

Publication types

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

MeSH terms

  • Aldehydes / chemical synthesis
  • Aldehydes / chemistry*
  • Alkadienes / chemistry*
  • Alkynes / chemistry
  • Catalysis
  • Ketones / chemical synthesis
  • Ketones / chemistry*
  • Methane / analogs & derivatives*
  • Methane / chemistry
  • Nitroparaffins / chemistry*
  • Phosphines / chemistry

Substances

  • Aldehydes
  • Alkadienes
  • Alkynes
  • Ketones
  • Nitroparaffins
  • Phosphines
  • propadiene
  • phosphine
  • Methane
  • nitromethane