Abstract
This chapter aims to provide an overview of stereoselective CS bond formations that centered around three classes of hydrocarbon compounds: alkynes, alkenes, and alkanes. The stereoselective functionalization of alkynes is reviewed in the context of hydrothiolation, bisthiolation, and carbothiolation that necessitate transition metal and Brønsted acid catalysis. The next section covers the thiofunctionalization of electron‐rich and electron‐poor alkenes through sulfetheration and conjugate addition reactions, in which the roles of Lewis acid and Brønsted acid catalysts are discussed in detail. The last section is centered on the use of alkanes in the stereoselectiveS‐alkylation catalyzed by transition metal and organocatalysis.