Guo Tenglong, Tang Nanfang, Lin Feng, Shang Qinghao, Chen Shuai, Qi Haifeng, Pan Xiaoli, Wu Chuntian, Xu Guoliang, Zhang Jian, Xu Dezhu, Cong Yu
CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, P.R. China.
Dalian Nationalities University, Dalian, 116600, P.R. China.
ChemSusChem. 2020 Jun 19;13(12):3115-3121. doi: 10.1002/cssc.202000536. Epub 2020 May 12.
Single-atom catalysts (SACs) as a bridge between hetero- and homogeneous catalysis have attracted much attention. However, it is still challenging to generate stable single atoms with high metal loadings, and the application of SACs in traditionally homogeneous catalytic reactions is highly desirable. Herein, a Cu SAC with a high Cu loading of 8.7 wt % supported on coordinatively unsaturated Al O was prepared and used in the amine-free synthesis of homoallylboranes. Up to 99 % conversion, 95 % 1,4-selective boration of the enals, and 48-68 % isolated yields of homoallylboranes were achieved, equaling the results of reported homogenous catalysts, and the system was more efficient and stable than nano Cu/γ-Al O . Mechanistic investigation indicated that Cu-Bpin species are the active intermediates of selective boration. The superior catalytic and recycling performance of Cu SAC paves an efficient and green path toward selective synthesis of homoallyborane fine chemicals.
单原子催化剂（SACs）作为多相催化和均相催化之间的桥梁，已引起广泛关注。然而，制备具有高金属负载量的稳定单原子仍然具有挑战性，并且SACs在传统均相催化反应中的应用备受期待。在此，制备了一种负载在配位不饱和AlO上的高Cu负载量为8.7 wt%的Cu SAC，并将其用于无胺合成高烯丙基硼烷。实现了高达99%的转化率、95%的烯醛1,4-选择性硼化以及48-68%的高烯丙基硼烷分离产率，与报道的均相催化剂结果相当，并且该体系比纳米Cu/γ-AlO更高效、更稳定。机理研究表明，Cu-Bpin物种是选择性硼化的活性中间体。Cu SAC优异的催化和循环性能为高烯丙基硼烷精细化学品的选择性合成开辟了一条高效、绿色的途径。
