Density-functional theory has been applied to the study of the mechanism of the Diels−Alder reaction of butadiene and ethylene. Both synchronous concerted and two-step diradical mechanisms were studied at the Becke3LYP/6-31G* level. The lowest energy stepwise pathway has a free energy of activation 7.7 kcal/mol above that of the concerted path. Spin correction of the spin-contaminated diradical transition structure energy reduces this energy difference to 2.3 kcal/mol. A study of the H2 potential energy surface suggests that the spin-projection procedure overcorrects the energies of diradical species; the diradical energies likely fall between the corrected and uncorrected values. Thus, the free energy of concert for the Diels−Alder reaction is predicted to be between 2.3 and 7.7 kcal/mol, in excellent agreement with thermochemical estimates. Energies of reaction and geometries of the reactants and product are in good agreement with available experimental results. Calculated secondary kinetic isotope effects agree well with experimental data on a related reaction, and support a concerted mechanism for the butadiene plus ethylene Diels−Alder reaction. The Becke3LYP DFT method is capable of relatively economical direct comparisons of concerted and stepwise mechanisms.

The conformations and electrostatic potentials of phosphonamides, phosphonamidates and sulfonamides have been compared to the tetrahedral intermediate for base-catalyzed amide hydrolysis. The wide variation in inhibition by these similar compounds is explained through differences in electrostatic effects.

The potential cycloaddition reactions between cyclopentadiene and cycloheptatriene have been explored theoretically. B3LYP/6-31G was used to locate the transition states, intermediates, and products for concerted pathways and stepwise pathways passing through diradical intermediates. Interconversions of various cycloadducts through sigmatropic shifts were also explored. CASPT2/6-31G single point calculations were employed to obtain independent activation energy estimates. MM3 was also used to compute reaction energetics. Several bispericyclic cycloadditions in which two cycloadducts are linked by a sigmatropic shift have been identified. B3LYP predicts, in line with frontier molecular orbital predictions, that the [6+4] cycloaddition is the favored concerted pathway, but an alternative [4+2] pathway is very close in energy. By contrast, CASPT2 predicts that a [4+2] cycloaddition is the preferred pathway. B3LYP predicts that the lowest energy path to many of the cycloadducts will involve diradical intermediates, whereas CASPT2 predicts that each of the products of orbital symmetry allowed reactions will be reached most readily by closed shell processes-concerted cycloadditions and sigmatropic shift rearrangements of cycloadducts.