Ji Cheng-Long, Chen Hongliang, Gao Qi, Han Jie, Li Weipeng, Xie Jin
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, 210023, China.
Nat Commun. 2024 May 2;15(1):3721. doi: 10.1038/s41467-024-48085-8.
The enormous and widespread use of organoboronic acids has prompted the development of innovative synthetic methodologies to meet the demands on structural diversity and functional group tolerance. The existing photoinduced defunctionalization radical borylation, typically focused on the conversion of one C-X bond (X= Br, I, or other leaving group) into only one C-B bond. Herein, we disclose a divergent radical dechloroborylation reaction enabled by dinuclear gold catalysis with visible light irradiation. A wide range of structurally diverse alkyl boronic, α-chloroboronic, and gem-diboronic esters can be synthesized in moderate to good yields (up to 92%). Its synthetic robustness is further demonstrated on a preparative scale and applied to late-stage diversification of complex molecules. The process hinges on a C-Cl bond relay activation in readily available gem-dichloroalkanes through inner-sphere electron transfer, overcoming the redox potential limits of unreactive alkyl chlorides.
有机硼酸的广泛大量使用促使了创新合成方法的发展，以满足对结构多样性和官能团耐受性的需求。现有的光诱导去官能团自由基硼化反应，通常只专注于将一个C-X键（X = Br、I或其他离去基团）转化为仅一个C-B键。在此，我们报道了一种由双核金催化并通过可见光照射实现的发散性自由基脱氯硼化反应。可以以中等至良好的产率（高达92%）合成多种结构多样的烷基硼酸酯、α-氯硼酸酯和偕二硼酸酯。其合成稳健性在制备规模上得到进一步证明，并应用于复杂分子的后期多样化。该过程依赖于通过内球电子转移对易得的偕二氯烷烃中的C-Cl键进行接力活化，克服了惰性烷基氯化物的氧化还原电位限制。
