Elsevier

Tetrahedron Letters

Volume 44, Issue 32, 4 August 2003, Pages 6133-6136
Tetrahedron Letters

H-abstraction prevails over α-cleavage in the solution and solid state photochemistry of cis-2,6-di(1-cyclohexenyl)cyclohexanone

https://doi.org/10.1016/S0040-4039(03)01450-3Get rights and content

Abstract

The photochemistry of cis-2,6-di(1-cyclohexenyl)cyclohexanone was studied in solution and in crystals to determine its photoreactivity and chemoselectivity. Although 1,3-acyl shifts and the oxadi-π-methane rearrangement products are possible for the β,γ-unsaturated chromophore, an efficient intramolecular abstraction of an allylic γ-hydrogen and small amounts of α-cleavage and decarbonylation were observed. The mechanism of the Norrish type-II reaction and the selectivity of product formation were analyzed in terms of structural information obtained by X-ray diffraction analysis.

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Acknowledgements

This work was supported by the NSF through grants CHE0242270 and CHE0116853 (Grant for the 600 MHz NMR). Graduate support to L.M.C. by the NSF and the Paul and Daisy Soros Fellowship for new Americans are also gratefully acknowledged.

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