Diels-Alder Reactions of 5-Alkyl-1,3-cyclopentadienes.
Facial selectivity in the Diels-Alder reactions of 1,3-cyclopentadienes substituted at C-5 by a variety of simple alkyl groups has been assessed with a number of dienophiles. The results are consistent with an explanation based on steric hindrance. Syn addition is more favored with sterically less demanding dienophiles. Diene 6, which is substituted at C-5 with methoxymethyl, shows a remarkable preference for syn addition with less encumbered dienophiles. This may indicate a conformational difference in its syn transition state relative to the transition states for addition syn to methyl, ethyl, or n-butyl substituents (dienes 1, 4, and 5). Dienophiles are more reluctant to add syn to the larger C-5 group with 1,2,3,4,5-pentamethyl-1,3-cyclopentadiene (2) and derivatives (3, and 7) and conformational effects become very important when C-5 bears two alkyl groups, as in dienes 3 and 7.
Letourneau
Johnathon E.
JE
Department of Chemistry, Memorial University of Newfoundland, St. John's, Newfoundland A1B 3X7, Canada.
Wellman
Mark A.
MA
Burnell
D. Jean
DJ