• Journal of Photoscience
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• v.12 no.3
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• pp.155-162
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• 2005

Results of studies of SET-promoted dipole-forming photochemical group transfer reactions of phthalimide and ${\alpha}-ketoamide$ derivatives are discussed. Azomethine ylide forming photochemical reactions, which are initiated by intramolecular SET from tethered silylmethyl-, carboxymethyl-, and ${\beta}-hydroxyethyl$ containing electron donors to excited states of phthalimides, related maleimides, and conjugated imides, are presented first. Following this, investigations of regioselective 1,4-dipole forming photochemical reactions of N-trialkylsilylmethyl- and N-trialkylstannyl-${\alpha}$-ketoamides are described.

• Journal of Photoscience
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• v.12 no.1
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• pp.47-50
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• 2005

Mediumeffects have been explored on the competitive H-atom abstraction and SET-promoted, silyl-transfer reactions of excited states of silylalkyl-substituted phenyl ketones. The chemical selectivities of photochemical reactions of silylalkyl phenyl ketones appear to depend on medium polarity, medium silophilicity, added metal cation and alkyl length. Irradiations of silylalkylketones in aqueous solvent system and in presence of metal cation such as $Li^+$ and $Mg^{+2} $lead to formation of acetophenone predominantly by the sequential SET-silyl transfer route.

• Bulletin of the Korean Chemical Society
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• v.31 no.9
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• pp.2453-2458
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• 2010

Photochemical studies of N-[(trimethylsilyl)alkyl]saccharins were carried out to investigate their photochemical behavior. Depending on the nature of the substrate and the solvent system employed, reactions of these substances can take place by either SET-promoted silyl migration from carbon to either the amide carbonyl or sulfonyl oxygen or by a N-S homolysis route. The results of the current studies show that an azomethine ylide, arising from a SET-promoted silyl migration pathway, is generated in photoreactions of N-[(trimethylsilyl)methyl]saccharin and this intermediate reacts to give various photoproducts depending on the conditions employed. In addition, irradiation of N-[(trimethylsily)ethyl]saccharin produces an excited state that reacts through two pathways, the relative importance is governed by solvent polarity and protic nature. Finally, photoirradiation of N-[(trimethylsilyl)propyl]saccharin in a highly polar solvent system comprised of 35% aqueous MeOH gives rise to formation of a tricyclic pyrrolizidine and saccharin that generated via competitive SET-promoted silyl transfer and $\gamma$-hydrogen abstraction pathways.