Symmetry-enforced conformational control of photochemical reactivity in 2-vinyl-1,3-terphenyl

Frederick D. Lewis; Xiaobing Zuo; Vladimir Gevorgyan; Michael Rubin

doi:10.1021/ja028251q

Symmetry-enforced conformational control of photochemical reactivity in 2-vinyl-1,3-terphenyl

Frederick D. Lewis^*, Xiaobing Zuo, Vladimir Gevorgyan, Michael Rubin

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

37 Scopus citations

Abstract

The photocyclization of o-vinylbiphenyl to 9,10-dihydrophenanthrene occurs with very low quantum yield because of the low ground-state population of the reactive syn rotamer. 2-Vinyl-1,3-terphenyl exists as a single rotamer which undergoes highly efficient photocyclization. Irradiation at 77 K in a rigid glass permits observation of the 8a,9-dihydrophenanthrene which rearranges to the 9,10-dihydrophenanthrene upon warming of the glass. The barriers for photocyclization and the thermal sigmatropic hydrogen shift are both remarkably small.

Original language	English (US)
Pages (from-to)	13664-13665
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	124
Issue number	46
DOIs	https://doi.org/10.1021/ja028251q
State	Published - Nov 20 2002

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja028251q

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title = "Symmetry-enforced conformational control of photochemical reactivity in 2-vinyl-1,3-terphenyl",

abstract = "The photocyclization of o-vinylbiphenyl to 9,10-dihydrophenanthrene occurs with very low quantum yield because of the low ground-state population of the reactive syn rotamer. 2-Vinyl-1,3-terphenyl exists as a single rotamer which undergoes highly efficient photocyclization. Irradiation at 77 K in a rigid glass permits observation of the 8a,9-dihydrophenanthrene which rearranges to the 9,10-dihydrophenanthrene upon warming of the glass. The barriers for photocyclization and the thermal sigmatropic hydrogen shift are both remarkably small.",

author = "Lewis, {Frederick D.} and Xiaobing Zuo and Vladimir Gevorgyan and Michael Rubin",

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T1 - Symmetry-enforced conformational control of photochemical reactivity in 2-vinyl-1,3-terphenyl

AU - Lewis, Frederick D.

AU - Zuo, Xiaobing

AU - Gevorgyan, Vladimir

AU - Rubin, Michael

PY - 2002/11/20

Y1 - 2002/11/20

N2 - The photocyclization of o-vinylbiphenyl to 9,10-dihydrophenanthrene occurs with very low quantum yield because of the low ground-state population of the reactive syn rotamer. 2-Vinyl-1,3-terphenyl exists as a single rotamer which undergoes highly efficient photocyclization. Irradiation at 77 K in a rigid glass permits observation of the 8a,9-dihydrophenanthrene which rearranges to the 9,10-dihydrophenanthrene upon warming of the glass. The barriers for photocyclization and the thermal sigmatropic hydrogen shift are both remarkably small.

AB - The photocyclization of o-vinylbiphenyl to 9,10-dihydrophenanthrene occurs with very low quantum yield because of the low ground-state population of the reactive syn rotamer. 2-Vinyl-1,3-terphenyl exists as a single rotamer which undergoes highly efficient photocyclization. Irradiation at 77 K in a rigid glass permits observation of the 8a,9-dihydrophenanthrene which rearranges to the 9,10-dihydrophenanthrene upon warming of the glass. The barriers for photocyclization and the thermal sigmatropic hydrogen shift are both remarkably small.

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ER -

Symmetry-enforced conformational control of photochemical reactivity in 2-vinyl-1,3-terphenyl

Abstract

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