Mechanistic aspects of the lycopodine Michael-Claisen domino cyclization

J Mol Model. 2014 Apr;20(4):2173. doi: 10.1007/s00894-014-2173-0. Epub 2014 Mar 16.

Abstract

The Michael-Claisen domino (MCD) cyclization used in the lycopodine synthesis by Stork, was evaluated mechanistically using DFT calculations. Calculations suggest that a dianion is not formed, which conforms to classical dianion formation normally requiring strong kinetic bases. Instead ethoxide in ethanol produces a monoanionic species driving the MCD cyclization. This endeavor has opened up potential to expand the scope of this unique reaction and provide educational clarity.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Alkaloids / chemistry*
  • Cyclization
  • Models, Chemical*
  • Models, Molecular
  • Quinolizines / chemistry*

Substances

  • Alkaloids
  • Quinolizines
  • lycopodine