The synthetic potential of phthalimide SET photochemistry

The authors' studies in the area of phthalimide photochemistry are discussed in the context of the development of new methods for N-heterocycle synthesis. Emphasis is given to reactions which are initiated by both intermolecular and intramolecular SET from silicon-containing electron donors to excited states of phthalimides and related maleimides and conjugated imides. The photoaddition and photocyclization processes which ensue follow mechanistic pathways, in which efficient desilylation of initially formed radical cation occurs to generate radical pair and biradical intermediates that serve as precursors of the products. Several examples that demonstrate the preparative potential of these reactions are presented. These are taken from the authors' investigations of (1) phthalimido-alkylsilane photocyclization reactions, (2) azomethine ylide-forming excited-state processes of N-(trimethylsilylmethyl)phthalimide, and (3) photoaddition and photocyclization reactions of phthalimide alpha-silyl ether, thioether, amine, and amide systems.