ISSN:
0020-7608
Keywords:
Computational Chemistry and Molecular Modeling
;
Atomic, Molecular and Optical Physics
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The ab initio MO and semiempirical multireference (MR) CI calculations were carried out to elucidate the energy differences between peroxy 1,4-diradical (DR) and 1,4-zwitterionic (ZWI) intermediates, which play crucial roles in photo-oxygenation reactions of nitrogen-activated C—C double bonds of enamines, indoles, and tryptamines. It is found that ZWI is more stable than DR in the case of electron-rich enamines. Protic solvents such as methanol are highly effective for the stabilization of ZWI by hydrogen bondings. From the present theoretical results, it is concluded that tryptophane undergoes the photooxidative cleavage reaction to give formylkynurenine under a specific condition, where polar solvents or catalysts sufficiently stabilize the ZWI state for the species.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/qua.560200212
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