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The typical definition of “stereochemistry” does not consider the centrality of quantum chemistryQuantum chemistry. Examples are provided herein involving stereochemical factors in the molecular orbital-based mechanism of pericyclic reactions—the Woodward–Hoffmann rulesWoodward-Hoffmann rules. Two molecular orbital tools used by Roald HoffmannHoffmann, Roald in the spring of 1965 to explain insightfully the stereospecificityStereospecificity of electrocyclizationsElectrocyclizations and sigmatropic reactionsSigmatropic reactions are explicated. An especially insightful moment in Hoffmann’s determination of the mechanism of sigmatropic reactions is discussed in detail. These analyses provide additional evidence that the seemingly simple determination of the orbitalSigma orbitals symmetryOrbital symmetry mechanism of pericyclic reactionsPericyclic reactions from the perspective of 2024 was extraordinarily complicated from the perspective of 1965. The expansion of the definition of stereochemistry to include quantum chemistry is recommended.

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Expansion of the Definition of “Stereochemistry” to Include Quantum Chemistry. When “Funny” is Fun but not Funny

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  • 发表日期：

    2025年

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  • Jeffrey I. Seeman

摘要

The typical definition of “stereochemistry” does not consider the centrality of quantum chemistryQuantum chemistry. Examples are provided herein involving stereochemical factors in the molecular orbital-based mechanism of pericyclic reactions—the Woodward–Hoffmann rulesWoodward-Hoffmann rules. Two molecular orbital tools used by Roald HoffmannHoffmann, Roald in the spring of 1965 to explain insightfully the stereospecificityStereospecificity of electrocyclizationsElectrocyclizations and sigmatropic reactionsSigmatropic reactions are explicated. An especially insightful moment in Hoffmann’s determination of the mechanism of sigmatropic reactions is discussed in detail. These analyses provide additional evidence that the seemingly simple determination of the orbitalSigma orbitals symmetryOrbital symmetry mechanism of pericyclic reactionsPericyclic reactions from the perspective of 2024 was extraordinarily complicated from the perspective of 1965. The expansion of the definition of stereochemistry to include quantum chemistry is recommended.