Intramolecular Diels−Alder Reactions of Ester-Linked 1,3,8-Nonatrienes

Tory N. Cayzer,† Michael N. Paddon-Row,*‡ Damian Moran,‡ Alan D. Payne,† Michael S. Sherburn,*† and Peter Turner§;
Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia, School of Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia, and School of Chemistry, University of Sydney, Sydney, NSW 2006, Australia
J. Org. Chem., 2005, 70 (14), pp 5561–5570
DOI: 10.1021/jo0505829
Publication Date (Web): June 16, 2005
Copyright © 2005 American Chemical Society
†

 Australian National University.

,
*

 Corresponding author.

,
‡

 The University of New South Wales.

,
§

 University of Sydney.

,

 Author to whom correspondence should be addressed regarding crystal structures: p.turner@chem.usyd.edu.au.

, sherburn@rsc.anu.edu.au, ; , m.paddonrow@unsw.edu.au

Abstract

Abstract Image

Penta-1,3-dienyl acrylates undergo kinetically controlled intramolecular Diels−Alder (IMDA) reactions and DFT calculations (B3LYP/6-31+G(d)) predict stereoselectivities that are in very good agreement with the experimental values. The nature of the diene C1 substituent has virtually no influence upon reactivity or trans/cis-stereoselectivity whereas terminal C9 dienophile substituents have a substantial effect on both the reactivity and stereoselectivity of these IMDA reactions. The TSs highlight contributions from strain in the developing tether-containing ring, and steric and electronic effects between tether and dienophile substituents, thus providing insight into the origins of IMDA reactivity and stereoselectivity.

View: Full Text HTML | Hi-Res PDF

Tools

History

  • Published In Issue July 08, 2005
  • Received March 22, 2005

Recommend & Share

Related Content

Other ACS content by these authors: