A Covalent Triazine Framework for Photocatalytic Anti‐Markovnikov Hydrofunctionalizations

Abstract Porous materials‐based heterogeneous photocatalysts, performing selective organic transformations, are increasing the applicability of photocatalytic reactions due to their ability to merge traditional photocatalysis with structured pores densely decorated with catalytic moiety for efficient mass and charge transfer, as well as added recyclability. We herein disclose a porous crystalline covalent triazine framework (CTF)‐based heterogeneous photocatalyst that exhibits excellent photoredox properties for different hydrofunctionalization reactions such as hydrocarboxylations, hydroamination and hydroazidations. The high oxidizing property of this CTF enables the activation of styrenes, followed by regioselective C−N and C−O bond formation at ambient conditions. A change in the physicochemical and optoelectronic properties of the CTF, upon protonation during catalysis, lies at the basis of its photocatalytic properties. This allows us to obtain hydrocarboxylations, hydroamination, and hydroazidations from a myriad of electron‐donating and ‐withdrawing aromatic and aliphatic substrates. This catalytic approach is further extended to late‐stage functionalization of bio‐active molecules. Finally, detailed characterizations of the CTF and further mechanistic investigations provide mechanistic insights into these reactions.