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Keywords:

  • activation strain model;
  • cycloaddition;
  • Diels;
  • Alder reaction;
  • endo rule;
  • density functional theory calculations;
  • reactivity

Detailed density functional theory calculations definitively rationalize the preference for the endo cycloadduct (also known as endo rule) in text-book thermal Diels–Alder reactions involving maleic anhydride and cyclopentadiene or butadiene. This selectivity is mainly caused by an unfavorable steric arrangement in the transition-state region of the exo pathway which translates into a more destabilizing activation strain. In contrast with the widely accepted, orbital-interaction-based explanation for the endo rule, it is found that neither the orbital interactions nor the total interaction between the deformed reactants contributes to the endo selectivity. © 2013 Wiley Periodicals, Inc.