Rhodium-catalyzed intramolecular formation of N-sulfamoyl 2,3-aziridino-γ-lactones and their use for the enantiospecific synthesis of α,β-diamino acid derivatives

J Org Chem. 2012 Jul 6;77(13):5592-9. doi: 10.1021/jo300468j. Epub 2012 Jun 13.

Abstract

4-Hydroxymethylbutenolide 4 was transformed into its sulfamoyl derivative 5, which upon treatment with iodosobenzene diacetate and magnesium oxide in the presence of a rhodium catalyst afforded the product of intramolecular aziridination 6. Reaction of 6 with primary or secondary amines in DMA led to regioselective opening of the aziridine ring at C2 to give the corresponding bicyclic derivatives 7a-7g in good to excellent yields. Methanolysis of the lactone ring of the N-benzyl-N-methyl derivative 7c followed by protection of the resulting secondary hydroxy group and treatment of the product with Boc anhydride provided the activated cyclic sulfamates 13 and 14. The latter then reacted with a second nucleophile (azide or thiophenol) to give the corresponding difunctionalized α,β-diamino methyl esters 15-18, 20.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Amino Acids, Diamino / chemical synthesis*
  • Amino Acids, Diamino / chemistry
  • Catalysis
  • Lactones / chemical synthesis*
  • Lactones / chemistry
  • Molecular Structure
  • Organometallic Compounds / chemistry*
  • Rhodium / chemistry*
  • Stereoisomerism

Substances

  • Amino Acids, Diamino
  • Lactones
  • Organometallic Compounds
  • Rhodium