Tian Ximei, Wu Lipeng
State Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences Lanzhou 730000 P. R. China
University of Chinese Academy of Sciences Beijing 100049 P. R. China.
Chem Sci. 2025 Mar 12;16(15):6515-6521. doi: 10.1039/d5sc01132a. eCollection 2025 Apr 9.
Cyclic boronates are versatile synthons for organic synthesis and for introducing ring systems into bioactive molecules. Existing synthetic methods have narrow substrate scope and the synthesis of α-substituted cyclic boronates is still elusive. Furthermore, no general method for synthesizing cyclic boronates with different ring sizes and hetero atom containing rings is available. Herein, we present a new and general synthetic method for synthesizing α-substituted cyclic boronates. Our approach has the advantage of using earth-abundant Ti as the catalyst and readily available dihaloalkanes, such as dichloromethane, as the reactant. Cyclic boronates that are otherwise difficult to access, such as α-substituted cyclic boronates with three-, four-, five-, and six-membered rings, heteroatom-containing rings, and cyclic boronates with spiro rings, are readily obtained.
环状硼酸酯是有机合成以及将环系引入生物活性分子中的通用合成子。现有的合成方法底物范围狭窄，α-取代环状硼酸酯的合成仍然难以实现。此外，尚无合成具有不同环大小和含杂原子环的环状硼酸酯的通用方法。在此，我们提出了一种合成α-取代环状硼酸酯的全新通用合成方法。我们的方法具有以下优点：使用地壳中储量丰富的钛作为催化剂，并使用容易获得的二卤代烷烃（如二氯甲烷）作为反应物。否则难以获得的环状硼酸酯，如具有三元、四元、五元、六元环的α-取代环状硼酸酯、含杂原子环的环状硼酸酯以及具有螺环的环状硼酸酯，都能够轻松获得。
