title: Impact of Lewis acids on Diels-Alder reaction reactivity: a conceptual density functional theory study.
abstract: Density functional theory (DFT) and conceptual/chemical DFT studies are carried out in this work for the normal electron demand Diels-Alder reaction between isoprene and acrolein to compare chemical reactivity and regioselectivity of the reactants in the absence and presence of Lewis acid (LA) catalysts. A cyclic coplanar structure of acrolein-LA complex has been observed and the natural bond orbital analysis has been employed to interpret the interaction between acrolein and LAs. Reactivity indices from frontier molecular orbital energies are proved to be adequate and efficient to evaluate the catalytic property of LAs. Linear relationships have been discovered among the bond order, bond length, catalytic activation, and chemical reactivity for the systems concerned. The validity and applicability of maximum hardness principle, minimum polarizability principle, and minimum electrophilicity principle are examined and discussed in the prediction of the major regioselective isomer and the preferred reaction pathway for the reactions in the present study.
authors.affiliation: Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research, Ministry of Education, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081, P. R. China.
authors.forename: Yue
authors.initials: Y
authors.lastname: Xia
authors.forename: Dulin
authors.initials: D
authors.lastname: Yin
authors.forename: Chunying
authors.initials: C
authors.lastname: Rong
authors.forename: Qiong
authors.initials: Q
authors.lastname: Xu
authors.forename: Donghong
authors.initials: D
authors.lastname: Yin
authors.forename: Shubin
authors.initials: S
authors.lastname: Liu
mesh_terms: D000171:Acrolein / Q000737:chemistry; D002070:Butadienes / Q000737:chemistry; D002712:Chlorides / Q000737:chemistry; D045782:Hemiterpenes / Q000737:chemistry; D010420:Pentanes / Q000737:chemistry; D011789:Quantum Theory; D015203:Reproducibility of Results
chemical_list: D002070:Butadienes; D002712:Chlorides; D045782:Hemiterpenes; D010420:Pentanes; C005059:isoprene; D000171:Acrolein