A Theoretical Comparison of Two Competing Diradical Cyclizations in Enyne-Allenes:  The Myers−Saito and the Novel C2−C6 Cyclization

The reaction mechanism and the energetics of the C2−C7 and of the C2−C6 cyclization of (Z)-1,2,4-heptatriene-6-yne are studied employing large scale MR-CI calculations. In addition the influence of vibrational motions and of temperature corrections on the barrier height of both reactions is estimate...

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Bibliographic Details
Published in:Journal of the American Chemical Society 1998-07, Vol.120 (25), p.6356-6361
Main Authors: Engels, B, Hanrath, M
Format: Article
Language:English
Online Access:Get full text
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Summary:The reaction mechanism and the energetics of the C2−C7 and of the C2−C6 cyclization of (Z)-1,2,4-heptatriene-6-yne are studied employing large scale MR-CI calculations. In addition the influence of vibrational motions and of temperature corrections on the barrier height of both reactions is estimated. For both products the first excited electronic states are computed to estimate possible switches from diradical to zwitterionic reaction mechanism.
ISSN:0002-7863
1520-5126
DOI:10.1021/ja973051d