Premium
Alder‐ene reaction: Aromaticity and activation‐strain analysis
Author(s) -
Fernández Israel,
Bickelhaupt F. Matthias
Publication year - 2011
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.22877
Subject(s) - reactivity (psychology) , chemistry , ene reaction , propene , transition state , strain (injury) , activation barrier , aromaticity , density functional theory , computational chemistry , medicinal chemistry , stereochemistry , molecule , catalysis , organic chemistry , medicine , alternative medicine , pathology
We have computationally explored the trend in reactivity of the Alder‐ene reactions between propene and a series of seven enophiles using density functional theory at M06‐2X/def2‐TZVPP. The reaction barrier decreases along the enophiles in the order H 2 CCH 2 > HCCH > H 2 CNH > H 2 CCH(COOCH 3 ) > H 2 CO > H 2 CPH > H 2 CS. Thus, barriers drop in particular, if third‐period atoms become involved in the double bond of the enophile. Activation‐strain analyses show that this trend in reactivity correlates with the activation strain associated with deforming reactants from their equilibrium structure to the geometry they adopt in the transition state. We discuss the origin of this trend and its relationship with the extent of synchronicity between H transfer from ene to enophile and the formation of the new CC bond. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011