Unraveling polar Diels-Alder reactions with conceptual DFT analysis and the distortion/interaction model

作者：Sarotti Ariel M^*

来源：Organic and Biomolecular Chemistry, 2014, 12(1): 187-199.

DOI：10.1039/c3ob41628c

The reaction energetics of 280 polar Diets-Alder (DA) reactions between 70 dienophiles and 4-dienes have been studied in detail using the B3LYP/6-31G* level of theory, combining conceptual density functional theory (DFT) analysis and the distortion/interaction model. The barrier heights are governed by a fine balance between the energy required to distort the reactants from their initial to their transition state geometries (Delta E-d double dagger) and the binding energy between the deformed reactants in the TS (Delta E-i double dagger). The Delta E-i double dagger values strongly correlate with the electrophilicity index, omega, which measures the stabilization energy when the system acquires an additional electronic charge from the environment, whereas the Delta E-d double dagger was found to depend mainly on the nature of the diene, structural parameters of the dienophile (degree of substitution and ring size) and the asynchronicity of the TS. A detailed analysis to account for the geometrical parameters of the strained diene and dienophile moieties that influence the energy strain of the distorted fragments is also reported.

• 出版日期2014-1-7