We report a photocatalyst-free, visible-light-driven cross-dehydrogenative coupling protocol for the direct C3-phosphorothiolation of indoles, using inexpensive KI as catalyst and atmospheric oxygen as oxidant. This transition-metal-free method avoids the use of hazardous peroxides and malodorous thiols, enabling the utilization of odorless O,O-diethyl S-hydrogen phosphorothioate and unfunctionalized indoles with good practicability. The obtained phosphorothiolated indoles are readily converted to diverse dithio-functionalized compounds. This operationally simple, sustainable method provides a practical platform for green C–H phosphorothiolation.
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Chen et al. (2026) studied this question.
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