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

Abstract

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.