Woodward–Hoffmann rules

Common card · No. 391449

The Woodward–Hoffmann rules (or the pericyclic selection rules) are a set of rules devised by Robert Burns Woodward and Roald Hoffmann to rationalize or predict certain aspects of the stereochemistry and activation energy of pericyclic reactions, an important class of reactions in organic chemistry. The rules originate in certain symmetries of the molecule's orbital structure that any molecular Hamiltonian conserves. Consequently, any symmetry-violating reaction must couple extensively to the environment; this imposes an energy barrier on its occurrence, and such reactions are called symmetry-forbidden. Their opposites are symmetry-allowed. Although the symmetry-imposed barrier is often formidable (up to c. 5 eV or 480 kJ/mol in the case of a forbidden [2+2] cycloaddition), the prohibition is not absolute, and symmetry-forbidden reactions can still take place if other factors (e.g. strain release) favor the reaction. Likewise, a symmetry-allowed reaction may be preempted by an insurmountable...

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