Supported Lanthanum Borohydride Catalyzes CH Borylation Inside Zeolite Micropores

Angew Chem Int Ed Engl. 2022 Apr 4;61(15):e202117394. doi: 10.1002/anie.202117394. Epub 2022 Feb 18.

Abstract

The zeolite-supported lanthanide La(BH4 )x -HY30 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.

Keywords: Borylation; C−H Activation; Rare-Earth Elements; Supported Organometallic Catalysts; Zeolite.