Incorporation of Chiral Frustrated Lewis Pair into Metal-Organic Framework with Tailored Microenvironment for Heterogeneous Enantio- and Chemoselective Hydrogenation

The incorporation of a chiral frustratedLewis pair intoa metal-organic framework with a tailored microenvironmentcreates enzyme-mimic regions that realize enantio- and chemoselectivehydrogenation. The development ofefficient heterogeneous catalysts with multiselectivity(e.g., enantio- and chemoselectivity) has long been sought after butwith limited progress being made so far. To achieve enantio- and chemoselectivityin a heterogeneous system, as inspired by enzymes, we illustrate hereinan approach of creating an enzyme-mimic region (EMR) within the nanospaceof a metal-organic framework (MOF) as exemplified in the contextof incorporating a chiral frustrated Lewis pair (CFLP) into a MOFwith a tailored pore environment. Due to the high density of the EMRfeaturing the active site of CFLP and auxiliary sites of the hydroxylgroup/open metal site within the vicinity of CFLP, the resultant EMR@MOFdemonstrated excellent catalysis performance in heterogeneous hydrogenationof & alpha;,& beta;-unsaturated imines to afford chiral & beta;-unsaturatedamines with high yields and high enantio- and chemoselectivity. Therole of the hydroxyl group/open metal site in regulating chemoselectivitywas proved by the observation of a catalyst-substrate interactionexperimentally, which was also rationalized by computational results.This work not only contributes a MOF as a new platform for multiselectivecatalysis but also opens a promising avenue to develop heterogeneouscatalysts with multiselectivity for challenging yet important transformations.

Automated summary

The incorporation of a chiral frustrated Lewis pair into a metal-organic framework creates enzyme-mimic regions that exhibit enantio- and chemoselective hydrogenation, providing a new approach for achieving multiselectivity in heterogeneous catalysis. The enzyme-mimic region in the metal-organic framework, which features the active site of the chiral frustrated Lewis pair and auxiliary sites within its vicinity, shows excellent catalysis performance with high yields and selectivity in the hydrogenation of & alpha;,& beta;-unsaturated imines. This work not only contributes a new platform for multiselective catalysis but also opens up possibilities for developing heterogeneous catalysts with multiselectivity for challenging transformations.