Toward an understanding of the selectivity in domino reactions. A DFT study of the reaction between acetylenedicarboxylic acid and 1, 3-Bis(2-furyl)propane
The mechanism of the domino reaction between acetylenedicarboxylic acid and 1,3-bis(2-furyl)propane has been theoretically studied in the framework of density functional theory. This domino process comprises two consecutive cycloaddition reactions: the first one is initialized by the nucleophilic attack of the C5 position of the furan ring to a conjugate position of acetylenedicarboxylic acid to give a zwitterionic intermediate, which by a subsequent ring-closure process affords an oxanorbornadiene intermediate. The second reaction is an intramolecular concerted cycloaddition of this intermediate to give the final dioxapentacyclic adduct. For the second cycloaddition, which corresponds to the step controlling the selectivity, eight alternative reaction pathways are found. Chemoselectivity, facial selectivity, and stereoselectivity of this domino reaction are related with the different approach modes of the tethered furan to the oxanorbornadiene system of the intermediate. The most favorable pathway takes place along an endo/syn approach of the furan ring relative to the bridged oxygen atom of the oxanorbornadiene system, with participation of the substituted double bond. An analysis of energetic contributions to the potential energy barriers for the intramolecular cycloadditions identifies the different factors controlling the reactive channels. Selectivity outcome is reproduced by these calculations.
Domingo
LR
Departamento de Quimica Organica, Universidad de Valencia, Dr. Moliner 50, 46100 Burjassot, Valencia, Spain, and Departament de Ciencies Experimentals, Universitat Jaume I, Apartat 224, 12080, Castello, Spain.
Picher
MT
Andres
J