Visible-light-driven TTST enables divergent synthesis of trifluoromethylated and trifluoromethylthiolated products through chemo- and regioselectivity

Abstract

A novel metal-free, additive-free, and mild synthetic strategy has been developed, which utilizes S-trifluoromethyl trifluoromethanesulfonate (TTST) as a multifunctional fluorine source under ambient conditions to achieve precise molecular modification. This study represents the first successful realization of dual control over the chemoselectivity and regioselectivity of TTST reagents, enabling the construction of a diverse molecular library that includes C2-trifluoromethyl indoles, C3-trifluoromethylthio indoles, trifluoromethylated heterocycles, and fused-ring trifluoromethylthio compounds. Through precise regulation of reaction pathways, we have established a TTST-based multi-level divergent synthesis platform. This system not only exhibits exceptional synthetic efficiency and broad substrate scope but also embodies significant green chemistry merits, such as mild reaction conditions, the absence of transition metal catalysts, and the avoidance of any additives.