The study of the stereochemistry of organic sulfur compounds has been ongoing for over a century, with S-chirogenic pharmacophores playing an essential role in drug discovery within bioscience and medicinal chemistry. Traditionally, the synthesis of sulfinamides featuring stereogenic sulfur(IV) centers involves a complex, multistep process that often depends on chiral auxiliaries or kinetic resolution. Here, we introduce an effective and versatile method for synthesizing diverse classes of S-chirogenic sulfinamides through selective aryl and alkenyl addition to sulfinylamines. This process is catalysed by a chiral nickel or cobalt complex under reductive conditions, and eliminating the need for preformed organometallic reagents. The method facilitates the incorporation of a diverse array of aryl and alkenyl halides at the sulfur position, enabling their integration into various biologically significant sulfur pharmacophores. Our detailed mechanistic investigations and density functional theory calculations provide insights into the reaction pathway, particularly highlighting the enantiocontrol mode during addition process.