N,N-diethyl O-carbamate: directed metalation group and orthogonal Suzuki-Miyaura cross-coupling partner

J Am Chem Soc. 2009 Dec 16;131(49):17750-2. doi: 10.1021/ja907700e.

Abstract

The first Suzuki-Miyaura cross-coupling of an aryl O-carbamate, a versatile and powerful directed metalation group (DMG) in directed ortho metalation (DoM) chemistry, is described using the inexpensive, bench-stable catalyst NiCl(2)(PCy(3))(2). Broad synthetic scope and good efficiency are demonstrated for aryl and heteroaryl O-carbamates. The role of water and hydrolysis equilibrium between free boronic acid and boroxine was established to be a crucial parameter for this transformation. When combined with DoM and traditional Pd-catalyzed Suzuki-Miyaura strategies, the methodology offers concise routes to uniquely substituted molecules, avoiding the need for protection/deprotection of the phenol and the use of strongly nucleophilic cross-coupling partners.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Carbamates / chemical synthesis*
  • Carbamates / chemistry
  • Molecular Structure
  • Stereoisomerism

Substances

  • Carbamates
  • N,N-diethyl O-carbamate