Efficient asymmetric synthesis of structurally diverse P-stereogenic phosphinamides for catalyst design

Angew Chem Int Ed Engl. 2015 Apr 27;54(18):5474-7. doi: 10.1002/anie.201500350. Epub 2015 Mar 10.

Abstract

The use of chiral phosphinamides is relatively unexplored because of the lack of a general method for the synthesis. Reported herein is the development of a general, efficient, and highly enantioselective method for the synthesis of structurally diverse P-stereogenic phosphinamides. The method relies on nucleophilic substitution of a chiral phosphinate derived from the versatile chiral phosphinyl transfer agent 1,3,2-benzoxazaphosphinine-2-oxide. These chiral phosphinamides were utilized for the first synthesis of readily tunable P-stereogenic Lewis base organocatalysts, which were used successfully for highly enantioselective catalysis.

Keywords: asymmetric catalysis; chirality; nucleophilic substitution; organocatalyst; phosphinamides.

MeSH terms

  • Amides / chemical synthesis*
  • Amides / chemistry
  • Chemistry Techniques, Synthetic
  • Lewis Bases / chemistry*
  • Molecular Structure
  • Phosphines / chemical synthesis*
  • Phosphines / chemistry
  • Phosphinic Acids / chemistry*
  • Stereoisomerism

Substances

  • Amides
  • Lewis Bases
  • Phosphines
  • Phosphinic Acids