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A Detailed Theoretical Analysis of the 1,7‐Sigmatropic Hydrogen Shift: The Möbius Character of the Eight‐Electron Transition Structure
Author(s) -
Jiao Haijun,
von Ragué Schleyer Paul
Publication year - 1993
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.199317631
Subject(s) - pericyclic reaction , character (mathematics) , chemistry , sigmatropic reaction , ab initio , computational chemistry , ring (chemistry) , benzene , electron , ab initio quantum chemistry methods , crystallography , physics , stereochemistry , molecule , nuclear physics , organic chemistry , geometry , mathematics
Pronounced aromatic character is found in the helical transition structure 1 for the 1,7 H shift in (Z,Z)‐1,3,5‐heptatriene according to ab initio calculations. The CC bond lengths are similar to those in benzene, the 1 H NMR shifts (IGLO calculations) indicate strong ring current effects, and the energy of concert (roughly 60 kcal mol −1 ) is the highest reported for any pericyclic reaction.