Sustainable Thioetherification via Electron Donor-Acceptor Photoactivation Using Thianthrenium Salts

The synthesis of sulfides has been widely studied because this functional subunit is prevalent in biomolecules and pharmaceuticals, as well as being a useful synthetic platform for further elaboration. Thus, various methods to build C-S bonds have been developed, but typically they require the use of precious metals or harsh conditions. Electron donor-acceptor (EDA) complex photoactivation strategies have emerged as versatile and sustainable ways to achieve C-S bond formation, avoiding challenges associated with previous methods. This work describes an open-to-air, photoinduced, site-selective C-H thioetherification from readily available reagents via EDA complex formation that tolerates a wide range of different functional groups. Moreover, C(sp(2))-halogen bonds remain intact using this protocol, allowing late-stage installation of the sulfide motif in various bioactive scaffolds, while allowing yet further modification through more traditional C-X bond cleavage protocols. Additionally, various mechanistic investigations support the envisioned EDA complex scenario.

Automated summary

This study developed a photoinduced, open-to-air C-H thioetherification method using readily available reagents, which tolerates various functional groups. The intact C(sp(2))-halogen bonds allow late-stage installation of sulfide motif and further modification with traditional C-X bond cleavage methods. Mechanistic investigations support the proposed electron donor-acceptor complex scenario.