Divergent regioselective synthesis of 2,5,6,7-tetrahydro-1H-1,4-diazepin-2-ones and 5H-1,4-benzodiazepines

J Org Chem. 2011 Oct 21;76(20):8320-8. doi: 10.1021/jo201497r. Epub 2011 Sep 27.

Abstract

A novel and simple one-pot synthesis of 3-substituted 2,5,6,7-tetrahydro-1H-1,4-diazepin-2-ones from 1,2-diaza-1,3-dienes (DDs) and N-unsubstituted aliphatic 1,3-diamines is described. Here we also report a procedure to selectively obtain alkyl 5H-1,4-benzodiazepine-3-carboxylates from the DDs and 2-aminobenzylamine. Both processes occur by means of sequential 1,4-conjugated addition followed by regioselective 7-exo cyclization. The behavior of N-methyl- and N,N'-dimethyl-1,3-diaminopropanes toward the DDs furnished pyrazol-3-ones and bis-α-aminohydrazones, respectively.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkanes / chemistry
  • Aza Compounds / chemistry
  • Benzodiazepines / analysis
  • Benzodiazepines / chemical synthesis*
  • Carboxylic Acids / chemistry
  • Chemistry, Pharmaceutical / methods*
  • Chromatography, Thin Layer
  • Cyclization
  • Diamines / analysis
  • Diamines / chemical synthesis*
  • Drug Discovery
  • Humans
  • Hydrazones / chemical synthesis
  • Magnetic Resonance Spectroscopy
  • Molecular Mimicry
  • Peptides / chemistry
  • Psychotropic Drugs / analysis
  • Psychotropic Drugs / chemical synthesis*
  • Pyrazolones / chemical synthesis
  • Stereoisomerism

Substances

  • Alkanes
  • Aza Compounds
  • Carboxylic Acids
  • Diamines
  • Hydrazones
  • Peptides
  • Psychotropic Drugs
  • Pyrazolones
  • Benzodiazepines