Visible-Light-Driven Photocatalytic Utilization of Sulfur Hexafluoride (SF₆) as an SF₅ Radical Source

Sulfur hexafluoride (SF₆) is a potent greenhouse gas widely used in industry, but its chemical inertness has limited its use as a source of pentafluorosulfanyl (SF₅) groups. We report herein a visible-light-driven photocatalytic transformation that enables SF₆ to function as an SF₅ radical source for the synthesis of SF₅ enamides under ambient pressure. Using ynamides as radical acceptors, a range of β-SF₅-substituted enamides were obtained under mild conditions in moderate to good yields. Mechanistic studies support the involvement of SF₅ radical intermediates and a hydrogen atom transfer process rather than a radical chain pathway. The resulting SF₅ enamides could be further transformed into diverse functionalized products, demonstrating their synthetic utility. This work highlights the potential of SF₆ as a practical SF₅ radical source for constructing valuable SF₅-containing organic molecules under photocatalytic conditions. This work provides a new strategy for the direct utilization of SF₆ in synthetic organic chemistry.