Critical distance model for the energy of activation of the Bergman cyclization of enediynes

The reaction profile of the Bergman cyclization of enediynes is written as a cubic polynomial expansion about the critical distance. Using the “simple sewing” approximation, a relationship is derived that expresses the energy of activation as a function of the critical distance, with the effect of o...

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Bibliographic Details
Published in:International journal of quantum chemistry 2003, Vol.95 (6), p.706-712
Main Authors: Gaffney, Shannon M., Capitani, Joseph F., Castaldo, Lyana, Mitra, Abhijit
Format: Article
Language:English
Subjects:
antitumor antibiotics
Bergman cyclization
critical distance model
enediynes
QSAR
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Summary:The reaction profile of the Bergman cyclization of enediynes is written as a cubic polynomial expansion about the critical distance. Using the “simple sewing” approximation, a relationship is derived that expresses the energy of activation as a function of the critical distance, with the effect of other geometric and electronic factors accounted for in the expansion coefficients. A training set of 10 representative enediynes were selected and input parameters were calculated by density functional theory at the B3LYP/6‐311G* level of theory. All calculations were corrected for zero‐point energy. All singlet biradical calculations were also checked for wave function stability. Calibration curves were then constructed that correlate the activation energy of cyclization of the molecules in the test set with the critical distance parameter. © 2003 Wiley Periodicals, Inc. Int J Quantum Chem, 2003
ISSN:0020-7608
1097-461X
DOI:10.1002/qua.10689