Homochiral Metal−Organic Frameworks for Heterogeneous Asymmetric Catalysis

Abstract

Homochiral crystallizations of two enantiomeric metal-organic frameworks (MOFs) Ce-MDIP1 and Ce-MDIP2 were achieved by using L- or D-BCIP as chiral inductions, respectively, where the chiralities were characterized by solid state CD spectra. Ce-MDIPs exhibit excellent catalytic activity and high enantioselectivity for the asymmetric cyanosilylation of aromatic aldehydes; the homochiral Cd-TBT MOF having L-PYI as a chiral adduct exhibits stereochemical catalysis toward the Aldol reactions.

Probing the bifunctional catalytic activity of ceria nanorods towards the cyanosilylation reaction

“…3 Cyanosilylation of carbonyl compounds with trimethylsilyl cyanide is an important C-C bond formation reaction because the products, cyanohydrins, can be transformed into many value-added chemicals with functional groups including a-hydroxycarbonyl compounds and b-amino alcohols. 5 To date, heterogeneous catalysts reported for the cyanosilylation reactions typically contain Lewis acid sites and/or Lewis base sites such as mesoporous aluminosilicates, 6 cerium-containing metal-organic framework catalysts 7 and solid acids. 8 Thus, cyanosilylation can serve as a useful reaction to study the acid-base active centers of catalysts.…”

Engineering chiral porous metal-organic frameworks for enantioselective adsorption and separation

“…In particular, chiral MOFs are highly promising for the separation of enantiomers and for chiral catalysis, as a result of their high porosity, functional diversity, flexibility and size and shape selectivity, surpassing traditional inorganic and organic porous materials [16][17][18][19][20] . Chiral MOF catalysts with uniform active sites for enantioselective reactions have been developed based on functionalized chiral molecular (pre)catalysts [21][22][23][24][25][26][27][28][29][30] . In a handful of latest studies, the resolution of enantiomers (racemic alcohols and sulphoxides) with chiral MOFs via chromatography [31][32][33][34] , crystallization [35][36][37][38][39][40] and membrane 41,42 has been reported, but only few exhibit good chiral separation performance.…”

Crystal structure of poly[aqua-(2,2′-bipyridine-κN,N′)-(μ4-5,5′-(hexane-1,6-diyl)-bis(oxy)diisophthalato κ8 O 1,O 2:O 3,O 4:O 5,O 6:O 7,O 8)manganese(II)], C21H

“…Metal-organic frameworks (MOFs) with boundless network structures have been a vibrant research field and aroused considerable attention from both academia and industry [1][2][3][4][5][6][7]. Theoretical predictions and network-based methods to regulate the network topology and geometries have been done to generate serviceable functional frameworks [8].…”

“…H4L and the corresponding deprotonated anions are expected to be vigoroso precursors for the construction of outstanding structures as they may admit various coordination modes [9]. The flexibility of the (−CH 2− ) 6 spacers and the existence of two methoxy groups will enable the carboxylic/carboxylate groups to coordinate metal ions in different directions [10][11][12]. On the other hand, the "mix-ligand" synthetic strategies also has become a research hotspot.…”