Functions Containing a Thiocarbonyl Group Bearing Two Heteroatoms Other Than a Halogen or Chalcogen

This chapter explores the chemistry of thiocarbonyl derivatives containing two heteroatoms other than halogens or chalcogens, emphasizing their synthesis, reactivity, and applications. For thiocarbonyl derivatives with nitrogen functionalities, key synthetic approaches include: (a) hydroamination of isothiocyanates, (b) catalytic transformations utilizing metals and nanohybrid frameworks, (c) mechanochemical methods, and (d) radical-mediated processes. Their production through asymmetric catalysis and sustainable synthetic pathways is also highlighted, alongside their roles as pharmaceutical drugs. For thiocarbonyl derivatives incorporating nitrogen-phosphorus bonds, the chapter details their synthesis via hydrophosphination catalyzed by zinc, titanium, and potassium complexes. These derivatives are shown to serve effectively as ligands in metal-catalyzed reactions, demonstrating broad functional group tolerance. Additionally, the preparation of thiocarbonyl derivatives with nitrogen-silicon and nitrogen-boron bonds is introduced, underscoring, respectively, their growing importance in organosilicon chemistry, heterocycle formation and catalysis. The chapter also provides a comprehensive outline of reaction mechanisms, including catalytic cycles, radical-mediated pathways, and stepwise transformations central to thiocarbonyl chemistry. It emphasizes innovative and green chemistry approaches, particularly water-based, solvent-free, and electrochemical synthesis techniques. Overall, this chapter highlights the versatility and significance of thiocarbonyl compounds in advancing organic synthesis, with extensive applications spanning pharmaceuticals, catalysis, and materials science.