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Mechanism of the Hetero‐Diels–Alder Reaction of Oxadienes and Alkenes: Calculation of the Acrolein/Ethene System
Author(s) -
Tietze Lutz F.,
Fennen Jens,
Anders Ernst
Publication year - 1989
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.198913711
Subject(s) - acrolein , diels–alder reaction , chemistry , reaction mechanism , computational chemistry , photochemistry , transition state , polar , organic chemistry , catalysis , physics , astronomy
The reaction profiles of the (hetero) Diels–Alder reactions acrolein + ethene [Eq. (a)] and butadiene + ethene are surprisingly different. Extensive AM1 /CI calculations revealed that, for reaction (a), the uncomplicated RHF method gave satisfactory results. RHF, UHF, and CI calculations gave only slightly differing results for the properties of the second transition state, which is generally rate‐determining. The existence of a polar‐radicaloid intermediate only slightly stabilized relative to the two transition states cannot be ruled out.