Theoretical and Experimental Determination of the Effects Governing the Transannular Diels−Alder Reaction of Trans−Trans−Cis Systems with or without Activation of the Dienophile

A thorough study of the transannular Diels-Alder (TADA) reaction of trans-trans-cis macrocyclic trienes was carried out. It led to a better understanding of various parameters that govern the TADA reaction in particular and the Diels-Alder reaction in general. Thus, carbonyl activation of the dienophile and substitution of the diene are discussed, as well as the presence of substituents on the macrocycle and their respective effects at the transition-state level.