A quantum chemical study on the mechanism of a photochemical [1,3]-hydroxyl shift in 2-propen-1-ol

G.J.M. Dormans, H.R. Fransen, H.M. Buck

Research output: Contribution to journalArticleAcademicpeer-review

14 Citations (Scopus)

Abstract

For the photochemical [1,3]-OH shift in 2-propen-1-01 a mechanism is proposed on the basis of the relaxation of the excited double bond toward a twisted geometry, accompanied by a separation of charge, leading to a planar [1,3]-OH shift. By means of semiempirical MNDO calculations followed by a limited (3 X 3) CI, one-dimensional potential energy surfaces for ground and excited states are calculated. It is shown that the proposed mechanism is strongly preferred to the mechanism predicted by the rules of conservation of orbital symmetry. It is to be expected that the presented results may be of general value in alkene photochemistry.
Original languageEnglish
Pages (from-to)1213-1216
JournalJournal of the American Chemical Society
Volume106
Issue number5
DOIs
Publication statusPublished - 1984

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