Diastereoselective synthesis of cyclopropane amino acids using diazo compounds generated in situ

J Org Chem. 2003 Nov 28;68(24):9433-40. doi: 10.1021/jo035060c.

Abstract

A simple and high-yielding method for the preparation of cyclopropane amino acids is described. The novel method involves the one-pot cyclopropanation of readily available dehydroamino acids using aryl and unsaturated diazo compounds generated in situ from the corresponding tosylhydrazone salts. It was found that thermal 1,3-dipolar cycloaddition followed by nitrogen extrusion gave the cyclopropane amino acid derivatives with good E selectivity, while reactions in the presence of meso-tetraphenylporphyrin iron chloride gave predominantly the corresponding Z isomers. The synthetic utility of this process was demonstrated in the synthesis of (+/-)-(Z)-2,3-methanophenylalanine [(+/-)-(Z)-1], the anti-Parkinson (+/-)-(E)-2,3-methano-m-tyrosine [(+/-)-(E)-2], and the natural product (+/-)-coronamic acid [(+/-)-3].

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amino Acids / chemical synthesis*
  • Amino Acids / chemistry
  • Cyclopropanes / chemical synthesis*
  • Cyclopropanes / chemistry
  • Diazonium Compounds / chemistry*
  • Models, Chemical
  • Molecular Structure
  • Stereoisomerism

Substances

  • Amino Acids
  • Cyclopropanes
  • Diazonium Compounds