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277. Chem. Sci., 2025,

date:2025-01-15

Photocatalytic [3 + 2]-annulation via sodium tetraarylborate: a fundamental approach for synthesizing 1,4,2-diazaborole analogs


Hao-Ni Qin, Hao-Wen Jiang, Yi Zhao, Saira Qurban, Ke-Chun Wang and Peng-Fei Xu *


https://doi.org/10.1039/D4SC08085H



Abstract

Substantial advancements have been achieved in the field of photocatalytic borylation utilizing 4c-7e Lewis base-boryl radicals. However, the utilization of 3c-5e neutral boryl radicals for CB bond formation remains relatively underexplored due to their inherent instability. In this study, we successfully demonstrated the direct construction of CB bonds using sodium tetraarylborate as a key reagent. This was accomplished by effectively stabilizing diaryl boryl radicals with nitrile compounds, thereby facilitating the synthesis of valuable boron-containing compounds. Overall, our research elucidates the significant role played by sodium tetraarylborate in enabling an efficient and versatile approach for synthesizing of 1,4,2- diazaborole analogs through a photocatalyzed [3 + 2]-annulation reaction. This mild and adaptable methodology expands synthetic strategies for obtaining diverse derivatives of 1,4,2-diazaboroles, with the RCNBAr2 complex serving as an effective boronnitrogen synthon that opens up pathways to multiple boronnitrogen heterocycles. Furthermore, this breakthrough significantly enhances the applicability of sodium tetraarylborate in photoredox catalysis.