Bond cleavage

Catalysis

Electron donor

Acceptor

Photochemistry

Materials science

Functional group

Electron acceptor

Biochemistry

Polymer

Combinatorial chemistry

Physics

Structural motif

Nanotechnology

Organic chemistry

Reagent

Condensed matter physics

Chemistry

Sulfide

Biomolecule

Angewandte Chemie International Edition

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(sp2 )-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.

Sustainable Thioetherification via Electron Donor–Acceptor Photoactivation Using Thianthrenium Salts