Photochemical tandem addition of water and oxygen to the alkene moiety of m-nitrostyrenes

doi:10.1016/1010-6030(89)87019-4

Journal of Photochemistry and Photobiology A: Chemistry

Volume 48, Issues 2–3, August 1989, Pages 387-396

https://doi.org/10.1016/1010-6030(89)87019-4 Get rights and content

Abstract

A new type of reaction involving the tandem photoaddition of water and oxygen to the alkene moiety of several m-nitrostyrenes in oxygenated aqueous solution via the triplet excited state, to give β-hydroxy-α-hydroperoxides, is reported. In the absence of oxygen, only anti-Markovnikov photohydration was observed. The proposed mechanism involves initial nucleophilic addition of water to the β-carbon of the alkene moiety in the triplet excited state, to generate a m-nitrobenzyl carbanion intermediate, which is subsequently “trapped” by oxygen when it is present in solution or is otherwise protonated by water. The quantum yields for the tandem addition and photohydration were identical (e.g. Φ = 0.32 for m-nitrostyrene), suggesting a common primary intermediate in the two pathways.

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¹: Natural Sciences and Engineering Research Council (NSERC) of Canada University Research Fellow, 1984 - 1989. Address correspondence to this author.

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Photochemical tandem addition of water and oxygen to the alkene moiety of m-nitrostyrenes

Abstract

Tetrahedron Lett.

Pure Appl. Chem.

J. Am. Chem. Soc.

Rev. Chem. Intermed.

Org. Photochem.

Can. J. Chem.

J. Am. Chem. Soc.