Photocycloaddition of four-carbon-tethered pyridones. Intramolecular hydrogen bonding and facilitated amide hydrolysis by a proximal secondary alcohol

J Org Chem. 2002 May 17;67(10):3487-93. doi: 10.1021/jo025565n.

Abstract

Four-carbon-tethered pyridones undergo photocycloaddition to give exclusively trans-[4 + 4] products. The presence of a tether alcohol engenders a solvent-dependent diastereoselectivity for the cycloaddition by intramolecular hydrogen bonding to the adjacent pyridone. Following cycloaddition, the alcohol can deliver a carbonyl group to the proximal, hindered amide nitrogen, leading to a very facile amide hydrolysis.

Publication types

  • Research Support, U.S. Gov't, P.H.S.

MeSH terms

  • Alcohols / chemistry*
  • Amides / chemistry*
  • Catalysis
  • Cyclization
  • Hydrogen Bonding
  • Hydrolysis
  • Ketones / chemistry
  • Models, Molecular
  • Molecular Conformation
  • Molecular Structure
  • Photochemistry
  • Pyridines / chemistry
  • Pyridines / radiation effects
  • Pyridones / chemistry*
  • Pyridones / radiation effects
  • Solvents
  • Stereoisomerism

Substances

  • Alcohols
  • Amides
  • Ketones
  • Pyridines
  • Pyridones
  • Solvents