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

doi:10.1021/ja00317a007

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

Department of Chemical Engineering and Chemistry

Research output: Contribution to journal › Article › Academic › peer-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 language	English
Pages (from-to)	1213-1216
Journal	Journal of the American Chemical Society
Volume	106
Issue number	5
DOIs	https://doi.org/10.1021/ja00317a007
Publication status	Published - 1984

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

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.",

author = "G.J.M. Dormans and H.R. Fransen and H.M. Buck",

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T1 - A quantum chemical study on the mechanism of a photochemical [1,3]-hydroxyl shift in 2-propen-1-ol

AU - Dormans, G.J.M.

AU - Fransen, H.R.

AU - Buck, H.M.

PY - 1984

Y1 - 1984

N2 - 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.

AB - 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.

U2 - 10.1021/ja00317a007

DO - 10.1021/ja00317a007

M3 - Article

VL - 106

SP - 1213

EP - 1216

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

SN - 0002-7863

IS - 5

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