We present a viable approach for the crossdehydrogenative coupling of Het-SF 4 -alkynes with tetrahydroisoquinolines under oxidative conditions, using TBHP and copper catalysts. These newly developed conditions boast enhanced yields and a more extensive range of substrates, demonstrating tolerance to various functional groups and addressing the limitations of earlier reports. Consequently, this method should increase opportunities for the exploration of SF 4 -containing compounds and their potential applications in drug discovery, materials science, and as alternatives to PFAS.