Theoretical secondary deuterium and primary C-14 kinetic isotope effects have been calculated for concerted and stepwise Diels-Alder reactions of butadiene with ethylene and acrolein. Comparisons between theory and experiment on substituted cases give definitive evidence for the mechanism and transition state geometries of the Diels-Alder reactions. Five levels of ab initio theory up to MCSCF/6-31G* are used for isotope effect calculations. The isotope effects for the retro-Diels-Alder reaction of ethanoanthracene are calculated and compared directly to experiment.
THEORETICAL SECONDARY KINETIC ISOTOPE EFFECTS AND THE INTERPRETATION OF TRANSITION-STATE GEOMETRIES .2. THE DIELS-ALDER REACTION TRANSITION-STATE GEOMETRY / J. STORER, L. RAIMONDI, K. HOUK. - In: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY. - ISSN 0002-7863. - 116:21(1994), pp. 9675-9683.
THEORETICAL SECONDARY KINETIC ISOTOPE EFFECTS AND THE INTERPRETATION OF TRANSITION-STATE GEOMETRIES .2. THE DIELS-ALDER REACTION TRANSITION-STATE GEOMETRY
L. RAIMONDISecondo
;
1994
Abstract
Theoretical secondary deuterium and primary C-14 kinetic isotope effects have been calculated for concerted and stepwise Diels-Alder reactions of butadiene with ethylene and acrolein. Comparisons between theory and experiment on substituted cases give definitive evidence for the mechanism and transition state geometries of the Diels-Alder reactions. Five levels of ab initio theory up to MCSCF/6-31G* are used for isotope effect calculations. The isotope effects for the retro-Diels-Alder reaction of ethanoanthracene are calculated and compared directly to experiment.
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