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

作者：Zhang, Yin; Jiang, Yao; Nafady, Ayman; Tang, Zhiyong^*; Al-Enizi, Abdullah M.; Tan, Kui; Ma, Shengqian^*

来源：ACS Central Science, 2023.

DOI：10.1021/acscentsci.3c00637

• FREE ASYMMETRIC HYDROGENATION
• RHODIUM-CATALYZED ALLYLATION
• AMINO
• CHEMISTRY
• HYDROAMINATION
• ALKYNES
• SCOPE
• BASE
• ACID
• FLP

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.