Li Yuting, Kanbur Uddhav, Cui Jinlei, Wang Guocang, Kobayashi Takeshi, Sadow Aaron D, Qi Long
U.S. DOE Ames Laboratory, Iowa State University, Ames, IA 50011, USA.
Department of Chemistry, Iowa State University, Ames, IA 50011, USA.
Angew Chem Int Ed Engl. 2022 Apr 4;61(15):e202117394. doi: 10.1002/anie.202117394. Epub 2022 Feb 18.
The zeolite-supported lanthanide La(BH ) -HY catalyzes C-H borylation of benzene with pinacolborane (HBpin), providing a complementary approach to precious, late transition metal-catalyzed borylations. The reactive catalytic species are generated from La grafted at the Brønsted acid sites (BAS) in micropores of the zeolite, whereas silanoate- and aluminoate-grafted sites are inactive under the reaction conditions. During typical catalytic borylations, conversion to phenyl pinacolborane (PhBpin) is zero-order in HBpin concentration. A turnover number (TON) of 167 is accessed by capping external silanols, selectively grafting at BAS sites, and adding HBpin slowly to the reaction.
沸石负载的镧系元素La(BH ) -HY催化苯与频哪醇硼烷(HBpin)的C-H硼化反应，为珍贵的后过渡金属催化硼化反应提供了一种补充方法。活性催化物种是由接枝在沸石微孔中的布朗斯特酸位点(BAS)上的镧生成的，而接枝有硅烷酸酯和铝酸酯的位点在反应条件下是无活性的。在典型的催化硼化反应中，转化为苯基频哪醇硼烷(PhBpin)的反应对HBpin浓度呈零级反应。通过封端外部硅醇、在BAS位点选择性接枝以及向反应中缓慢加入HBpin，可以实现167的转化数(TON)。
