A general leaving group assisted strategy for synthesis of pentafluorosulfanyl allylic compounds

Fluorine-containing allyl compounds are prevalent in drugs and bioactive molecules. Here, we report a straightforward and efficient radical pentafluorosulfanylation of allyl sulfones using sulfur chloride pentafluoride (SF(5)Cl) to synthesize structurally diverse pentafluorosulfanyl allylic compounds. This transformation exhibits excellent functional group tolerance and achieves an impressive isolated yield of up to 98% in just 1 minute under ultraviolet light. Mechanistic studies suggest that the sulfonyl group acts as a free radical leaving group, with the capability of abstracting the chlorine atom from SF(5)Cl. This radical chain propagation pathway facilitates the rapid regeneration of the sulfur pentafluoride radical, resulting in a notably high quantum yield. Moreover, this light-driven radical pentafluorosulfanylation simplifies the synthetic pathway to modify complex and bioactive molecules. In addition, the drug-modified pentafluorosulfanyl compounds exhibited promising effects in inhibiting cancer cell proliferation, both in vitro and in vivo. Therefore, this protocol provides a practical synthetic route to radical pentafluorosulfanylation, highlighting its potential in drug discovery.