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Regio- and stereoselectivity in light-induced [4+2]- and [2+2]-cycloadditions ofα-cyanoenamines to aromatic carbonyl compounds and hydrocarbons

  • “Applied Photochemistry”, Proceedings Of The 3rd Int. Conf. On Solar Energy Storage And Applied Photochemistry, Cairo, Eygpt, January 1995
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Abstract

α-Cyanoenamines with varied saturated azaheterocyclic amino groups are added to triplet excited 1-acylnaphthalenes in a highly regio-, stereo- and diastereo-selective manner forming 1,4-dihydro-1,4-ethanonaphthalenes in a [4+2]-mode. Replacement of the heterocyclic donor groups in the title compounds by open chain dialkylamino groups virtually eliminates the stereoselectivity in the [4+2]-addition. The latter reaction may be preceded and/or accompanied by an independent and both regio- and stereoselective [2+2]-addition. Similar striking selectivity phenomena are observed in the oxetane formation from aromatic 1,2-diketones andα-cyanoenamines. [2+2]-Photoadditions of the latter to naphthalene, phenanthrene, anthracene and acenaphthylene display reduced regio-, stereo- and diastereoselectivity in the cases studied at satisfactory preparative yields. These additions seem to be controlled by preferred singlet exciplex geometries.

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  1. Fachgebiet Organische Chemie, Gerhard-Mercator-Universität-GH Duisburg, D-47048, Duisburg, Germany

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Döpp, D. Regio- and stereoselectivity in light-induced [4+2]- and [2+2]-cycloadditions ofα-cyanoenamines to aromatic carbonyl compounds and hydrocarbons. Proc. Indian Acad. Sci. (Chem. Sci.) 107, 863–875 (1995). https://doi.org/10.1007/BF02869978

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