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[1,3], [3,3], and [3,5] Sigmatropic Rearrangements of Esters Are Pseudopericyclic
Author(s) -
Birney David M.,
Xu Xiaolian,
Ham Sihyun
Publication year - 1999
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/(sici)1521-3773(19990115)38:1/2<189::aid-anie189>3.0.co;2-v
Subject(s) - sigmatropic reaction , ab initio , cope rearrangement , computational chemistry , chemistry , symmetry (geometry) , stereochemistry , mathematics , organic chemistry , geometry
Allowed by orbital symmetry rules , the [3,5] sigmatropic ester rearrangement of ester 1 even has a lower barrier than a competing [3,3] rearrangement, according to ab initio calculations. This surprising result is a consequence of the lack of orbital overlap in the pseudopericyclic transition state.