Theoretical Study on the Molecular Mechanism of the Domino Cycloadditions between Dimethyl Acetylenedicarboxylate and Naphthaleno- and Anthracenofuranophane.
AM1, B3LYP/6-31G//AM1, and B3LYP/6-31G computational studies were performed to select the reaction pathway controlling the reactions between dimethyl acetylenedicarboxylate (DMAD) and two furanophanes, naphthalenofuranophane and anthracenofuranophane. For these domino reactions, several pathways have been characterized on the potential energy surface corresponding to two consecutive cycloadditions. The first step corresponds to a [4 + 2] intermolecular cycloaddition of DMAD with the furan ring or with the naphthalene or anthracene ring of both furanophane systems to yield an oxabicyclo[2.2.1]heptadiene or a bicyclo[2.2.2]octadiene intermediate, respectively. The second step corresponds to [4 + 2] intramolecular cycloadditions of these intermediates. For the naphthalenofuranophane, the most favorable reaction pathway takes place along the initial [4 + 2] intermolecular cycloaddition involving the nonsubstituted ring of the naphthalene system to give a benzobicyclo[2.2.2]octadiene intermediate, which by a [4 + 2] intramolecular cycloaddition between the substituted double bond of this intermediate and the furan ring affords the final cycloadduct. For the anthracenofuranophane, the most favorable reaction pathway takes place along the initial [4 + 2] intermolecular cycloaddition involving the furan ring to give an oxabicyclo[2.2.1]heptadiene intermediate, which by a [4 + 2] intramolecular cycloaddition between the nonsubtituted double bond of the bicyclic system and the naphthalene system affords the final cycloadduct. An analysis of energetic contributions to the potential energy barriers identifies the different factors controlling the competitive reaction pathways. The present theoretical results are able to explain the available experimental data.
Domingo
Luis R.
LR
Departamento de Química Orgánica, Universidad de Valencia, Dr. Moliner 50, 46100 Burjassot, Valencia, Spain, and Departament de Ciències Experimentals, Universitat Jaume I, Apartat 224, 12080 Castelló, Spain.
Picher
M. Teresa
MT
Andrés
Juan
J
Oliva
Mónica
M