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Density functional theory study of the regio‐ and stereoselectivity of diels–alder reactions of 5‐Aryl‐2‐pyrones
Author(s) -
Chemouri Hafida,
Mekelleche Sidi Mohamed
Publication year - 2011
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.23232
Subject(s) - chemistry , stereoselectivity , aryl , density functional theory , computational chemistry , potential energy surface , reaction mechanism , diels–alder reaction , concerted reaction , medicinal chemistry , stereochemistry , organic chemistry , molecule , catalysis , alkyl
A theoretical study of the mechanism and regio‐ and stereoselectivity of Diels–Alder reactions of 5‐aryl‐2‐pyrones (Ar = Ph, 4‐(MeS)‐Ph) with substituted alkenes (CHZ = CH 2 , Z = COMe, OAc) is performed at the B3LYP/6‐31G(d) level. The analysis of the relevant stationary points of the potential energy surface and intrinsic reaction coordinate calculations show that these cycloadditions are undergoing through asynchronous concerted mechanisms yielding to the formation of the 5‐endo isomers as the major cycloadducts. The calculation of activation and reaction energies indicates that the 5‐endo cycloadducts are favored both kinetically and thermodynamically. The obtained results are in good agreement with experimental outcomes. © 2011 Wiley Periodicals, Inc. Int J Quantum Chem, 2011