Investigations on the Suzuki-Miyaura and Negishi couplings with alkenyl phosphates: application to the synthesis of 1,1-disubstituted alkenes

J Org Chem. 2007 Aug 17;72(17):6464-72. doi: 10.1021/jo070912k. Epub 2007 Jul 14.

Abstract

The development of versatile Suzuki-Miyaura and Negishi cross-couplings with nonactivated alkenyl phosphates and aromatic boronic acids or organozinc reagents was achieved in acceptable to good yields. A series of 1,1-disubstituted alkenes were synthesized using a combination of either Ni(COD)2/Cy3P/K3PO4 or Pd2dba3/DPPF in THF. When working with alkenyl electrophiles in metal-catalyzed cross-couplings, this method lends itself as a less costly and more stable alternative to the corresponding triflate or nonaflate derivatives. In addition, initial studies are presented regarding an efficient 1,2-migration under Negishi coupling conditions.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkenes / chemical synthesis*
  • Gas Chromatography-Mass Spectrometry
  • Magnetic Resonance Spectroscopy
  • Phosphates / chemistry*

Substances

  • Alkenes
  • Phosphates