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Ab initio Theoretical Investigation of a Formal Alkene-Enedione Intramolecular [2 + 2] Photocyclization

Alan P. Marchand ; Department of Chemistry, University of North Texas, Denton, Texas 76203-5070, USA
Trevor D. Power ; Department of Chemistry, University of North Texas, Denton, Texas 76203-5070, USA
Hendrik G. Kruger ; School of Pure & Applied Chemistry, University of Natal, Durhan 4001, South Africa


Puni tekst: engleski pdf 81 Kb

str. 265-270

preuzimanja: 364

citiraj


Sažetak

Irradiation of 1 with visible light results in intramolecular [2 + 2] photocyclization to afford the corresponding pentacyclic cage diketone, i.e. pentacyclo [5.4.0.02,6.03,10.05,9]undecane-8,11-dione (2). The mechanism of this reaction has been scrutinized by using ab initio theoretical methods. The results of these calculations provide new evidence which supports earlier suggestions that alkene-enedione photocyclizations may actually proceed via a diradical stepwise mechanism through the triplet excited state rather than as concerted [2 + 2] cycloadditions.

Ključne riječi

photocyclization; intramolecular photocyclization; diketone; ab initio

Hrčak ID:

131812

URI

https://hrcak.srce.hr/131812

Datum izdavanja:

2.4.2001.

Posjeta: 937 *