6533b7d0fe1ef96bd125a1bd

RESEARCH PRODUCT

ChemInform Abstract: Influence of Reactant Polarity on the Course of the Inverse-Electron-Demand Diels-Alder Reaction. A DFT Study of Regio- and Stereoselectivity, Presence of Lewis Acid Catalyst, and Inclusion of Solvent Effects in the Reaction Between N

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The molecular mechanisms for the inverse-electron-demand Diels−Alder reactions between nitroethene and three substituted ethenes (propene, methyl vinyl ether, and dimethylvinylamine) to give the corresponding nitroso cycloadducts have been characterized with density functional theory methods using the B3LYP/6-31G* calculational level. On the basis of stability arguments and molecular orbital analysis relative rates, regioselectivity, and stereoselectivity, the presence of Lewis acid catalyst modeled by the BH3 system and the inclusion of solvent effects as a function of the nature of substituent in the dienophile fragment are analyzed and discussed. The ortho attack mode presents transition structures more stable than the meta one. For the former, reactivity, endo selectivity, and asynchronicity are enhanced with the increase of the electron-releasing character of the substituent on dienophile fragment. The reaction between nitroethene and propene has dissymmetric concerted transition structures associate...