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.
Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia.
Tory N
TN
Cayzer
Michael N
MN
Paddon-Row
Damian
D
Moran
Alan D
AD
Payne
Michael S
MS
Sherburn
Peter
P
Turner