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Volumn 48, Issue 16, 2009, Pages 2959-2963

A preferred disrotatory 4n electron möbius aromatic transition state for a thermal electrocyclic reaction

Author keywords

[No Author keywords available]

Indexed keywords

A-THERMAL; ELECTROCYCLIC REACTIONS; TOPOLOGY STRUCTURE; TRANSITION STATE; TRANSITION STRUCTURES; WOODWARD;

EID: 70349915881     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200806009     Document Type: Article
Times cited : (26)

References (67)
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    • We do not claim this to be a violation of the Woodward-Hoffmann rules, as these, focusing on the symmetry analysis of reactant and product, are consequently applied to structures that have symmetry elements. In contrast, the Dewar-Zimmerman interpretation applies to both symmetric and nonsymmetric transition-state structures. However, a topological orbital-mapping technique has been employed to show that the symmetry analysis can be replaced by a homeomorphic relationship between reactant and product topological spaces and that also applies to nonsymmetric molecules: see D. R. Kelsey, J. Comput. Chem. 1980,1, 3
    • We do not claim this to be a "violation" of the Woodward-Hoffmann rules, as these, focusing on the symmetry analysis of reactant and product, are consequently applied to structures that have symmetry elements. In contrast, the Dewar-Zimmerman interpretation applies to both symmetric and nonsymmetric transition-state structures. However, a topological orbital-mapping technique has been employed to show that the symmetry analysis can be replaced by a homeomorphic relationship between reactant and product topological spaces and that also applies to nonsymmetric molecules: see D. R. Kelsey, J. Comput. Chem. 1980,1, 3.
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    • In a basis orbital correlation diagram of a cyclically conjugated molecule, a "phase inversion" is denoted by an overlap of two individual orbital lobes with opposite signs. Two orbital phase inversions always annihilate and are equivalent to zero phase inversions in an MO with either the same number of nodal planes or a number of nodal planes incremented by one. A sign change inside an orbital (as in the delocalization pathway in the conrotatory transition state in 1,3,5,7-octatetraene, Figure lb) is not considered a phase inversion. Also see: M. J. S. Dewar, Angew. Chem. 1971, 83, 859; Angew. Chem. Int. Ed. Engl. 1971, 10, 761.
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    • It is interesting to note that terms "suprafacial" and "antara-facial" lose their accustomed meaning for a Möbius system with purely laticyclic orbital overlap and with a π system without distinguishable "faces". Please note that this is not "homotopy" (i.e. equivalence of faces).
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.