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We have investigated computationally a series of 18 Diels–Alder cycloadditions, involving four dienes (butadiene, 2-hydroxybutadiene, cyclopentadiene and cyclohexadiene) and variously-substituted ethylenes and acetylenes as dienophiles. It is demonstrated that the respective molecular electrostatic potentials can be used to provide insight into the initial modes of interaction of the dienes and dienophiles,...
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