Control elements in dynamically determined selectivity on a bifurcating surface.
The mechanism and the nature of the dynamically determined product selectivity in Diels-Alder cycloadditions of 3-methoxycarbonylcyclopentadienone (2) with 1,3-dienes was studied by a combination of product studies, experimental kinetic isotope effects, standard theoretical calculations, and quasiclassical trajectory calculations. The low-energy transition structures in these reactions are structurally balanced between [4pi(diene) + 2pi(dienone)] and the [2pi(diene) + 4pi(dienone)] modes of cycloaddition. The accuracy of these structures and their bispericyclic nature is supported by the experimental isotope effects. Trajectories passing through these transition structures can lead to both [4pi(diene) + 2pi(dienone)] and [2pi(diene) + 4pi(dienone)] cycloadducts, and the mixture of products obtained varies with the structure of the diene. The factors affecting this selectivity are analyzed. The geometry of the transition structure is a useful predictor of the major product, but the selectivity is also guided by the shape of the energy surface as trajectories approach the products and by how trajectories cross the transition state ridge.
Department of Chemistry, Texas A&M University, PO Box 30012, College Station, Texas 77842, USA.
Jacqueline B
JB
Thomas
Jack R
JR
Waas
Michael
M
Harmata
Daniel A
DA
Singleton
D000466:Alkadienes / Q000737:chemistry*; D001643:Bridged Bicyclo Compounds / Q000138:chemical synthesis / Q000737:chemistry; D055598:Chemical Phenomena; D003500:Cyclization; D003517:Cyclopentanes / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D007700:Kinetics; D008958:Models, Molecular; D013499:Surface Properties; D013816:Thermodynamics
D000466:Alkadienes; D001643:Bridged Bicyclo Compounds; D003517:Cyclopentanes; D007659:Ketones