Chiral Primary Amine-Catalyzed Asymmetric Photochemical Reactions of Pyridotriazoles with Boronic Acids to Access Triarylmethanes

Imine-containing azaarene-based triarylmethanes are vital molecular motifs that are prevalent in a wide array of bioactive compounds. Recognizing the limitations of current synthetic methodologies─marked by a scarcity of examples and difficulties in flexible functional group modulation─we have developed an efficient and modular asymmetric photochemical strategy employing pyridotriazoles and boronic acids as substrates. Utilizing novel chiral diamine-derived pyrroles and primary amines as catalysts, we successfully synthesized a diverse range of triarylmethanes with high yields and excellent enantioselectivities. This method not only exhibits a broad substrate scope and outstanding functional group tolerance but also enables the precise synthesis of deuterated derivatives using inexpensive D2O as the deuterium source. Mechanistic studies reveal that an unusual 1,4-boron shift is a critical step in generating the boronated enamine intermediate, while also shedding light on the potential enantiocontrol mechanisms facilitated by the chiral catalyst.