The formation of C–S bonds using cheap, stable and odorless sulfonyl chlorides and widely sourced and less toxic alcohols with the assistance of ADDP is reported. This method is suitable for a broad substrate scope and tolerates a broad range of functional groups. Additionally, our protocol provides a green and convenient methylating method utilizing methanol or methanol-d₄ and allows trideuteromethylthiolation with sulfonyl chlorides. This method can be applied for the late-stage diversification of natural products and drug analogs.