Intramolecular Diels-Alder reactions of ester-linked 1,3,8-nonatrienes.
[structures: see text] 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.
Cayzer
Tory N
TN
Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia.
Paddon-Row
Michael N
MN
Moran
Damian
D
Payne
Alan D
AD
Sherburn
Michael S
MS
Turner
Peter
P