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The Origin of the Halogen Effect on Reactivity and Reversibility of Diels–Alder Cycloadditions Involving Furan
Author(s) -
Pieniazek Susan N.,
Houk Kendall N.
Publication year - 2006
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/anie.200502677
Subject(s) - furan , halogen , cycloaddition , reactivity (psychology) , chemistry , generality , computational chemistry , alkylation , diels–alder reaction , organic chemistry , catalysis , alkyl , alternative medicine , pathology , psychology , psychotherapist , medicine
Origin and generality of the halogen effect in Diels–Alder reactions were explored with high‐accuracy CBS–QB3 computations. Halogen substitution increases cycloaddition exergonicities and decreases activation barriers. This effect is attributed to the energetic preference for electronegative halogen substituents to be attached to a more highly alkylated, and therefore more electropositive, carbon framework.