Photochemical Aspects of Thiocarbonyl Compounds in the Solid-State

Abstract

The field of organic solid-state photochemistry has become popular, and has been extended in recent years to a variety of new systems. In this chapter, the solid-state photochemical aspects of thiocarbonyl compounds are reviewed, which show considerably high photochemical reactivity toward [2+2] cycloaddition and hydrogen abstraction reactions. Excited thioimides react with alkenes in the solid state to give thietane-fused heterocycles. Thiones and thioimides abstract hydrogen intramolecularly in the solid state to make a new C–C bond. Oxidation of thiones by the solid–gas reaction gave the corresponding ketones. Some achiral materials crystallized in chiral space groups, and absolute asymmetric syntheses were performed using the chiral crystalline environment. These reactions can now be regarded as an important branch of organic chemistry. Furthermore, insight into the reaction mechanism that directly connects with X-ray crystallographic analysis is also described.