Further studies of intramolecular Michael reactions of nitrosoalkenes for construction of functionalized bridged ring systems

J Org Chem. 2011 Apr 1;76(7):2094-101. doi: 10.1021/jo1024392. Epub 2011 Feb 28.

Abstract

A wide variety of stabilized carbanions have been found to participate as nucleophiles in intramolecular Michael-type conjugate additions to in situ generated nitrosoalkenes to form bridged carbocyclic systems. The vinylnitroso platforms for these cyclizations have been prepared via two key steps involving ring-closing metathesis of vinyl chlorides and regioselective conversion of vinyl chlorides to α-chloroketones with sodium hypochlorite in glacial acetic acid/acetone. An alternative approach to preparation of some cyclization substrates has involved use of more reactive enol ethers as precursors to the requisite α-chloroketones. A sulfonamide anion has also been found to be an effective nucleophile in this type of reaction, leading to formation of a 6-azabicyclo[3.2.1]octane.

Publication types

  • Research Support, N.I.H., Extramural
  • Research Support, U.S. Gov't, Non-P.H.S.

MeSH terms

  • Anions / chemistry*
  • Azabicyclo Compounds / chemical synthesis*
  • Azabicyclo Compounds / chemistry*
  • Bridged-Ring Compounds / chemical synthesis*
  • Bridged-Ring Compounds / chemistry*
  • Cyclization
  • Cycloparaffins / chemistry*
  • Magnetic Resonance Spectroscopy
  • Molecular Structure
  • Nitroso Compounds / chemistry*
  • Stereoisomerism
  • Sulfonamides / chemistry*

Substances

  • 6-azabicyclo(3.2.1)octane
  • Anions
  • Azabicyclo Compounds
  • Bridged-Ring Compounds
  • Cycloparaffins
  • Nitroso Compounds
  • Sulfonamides