139224-72-9

Upstream product

• 7677-24-9 trimethylsilyl cyanide 
• 104-87-0 4-methyl-benzaldehyde 
• 589-18-4 4-Methylbenzyl alcohol 

Downstream Products

• 10017-04-6 2-hydroxy-2-p-tolylacetonitrile 
• 119904-34-6 (R)-(-)-1-cyano-1-(4-methylphenyl)methyl acetate 

Relevant academic research and scientific papers

Homochiral BINAPDA-Zr-MOF for Heterogeneous Asymmetric Cyanosilylation of Aldehydes

A new homochiral BINAPDA-Zr-MOF was prepared by a new chiral organic linker of (R)-4,4′-(6,6′-dichloro-2,2′-diethoxyl-[1,1′-binaphthalene]-4,4′-diyl)dibenzoic acid (R-L) and ZrCl4 under solvothermal conditions. Its structure was determined by P

Controlled Exchange of Achiral Linkers with Chiral Linkers in Zr-Based UiO-68 Metal-Organic Framework

The development of highly robust heterogeneous catalysts for broad asymmetric reactions has always been a subject of interest, but it remains a synthetic challenge. Here we demonstrated that highly stable metal-organic frameworks (MOFs) with potentially acid-labile chiral catalysts can be synthesized via postsynthetic exchange. Through a one- or two-step ligand exchange, a series of asymmetric metallosalen catalysts with the same or different metal centers are incorporated into a Zr-based UiO-68 MOF to form single- and mixed-M(salen) linker crystals, which cannot be accomplished by direct solvothermal synthesis. The resulting MOFs have been characterized by a variety of techniques including single-crystal X-ray diffraction, N2 sorption, CD, and SEM/TEM-EDS mapping. The single-M(salen) linker MOFs are active and efficient catalysts for asymmetric cyanosilylation of aldehydes, ring-opening of epoxides, oxidative kinetic resolution of secondary alcohols, and aminolysis of stilbene oxide, and the mixed-M(salen) linker variants are active for sequential asymmetric alkene epoxidation/epoxide ring-opening reactions. The chiral MOF catalysts are highly enantioselective and completely heterogeneous and recyclable, making them attractive catalysts for eco-friendly synthesis of fine chemicals. This work not only advances UiO-type MOFs as a new platform for heterogeneous asymmetric catalysis in a variety of syntheses but also provides an attractive strategy for designing robust and versatile heterogeneous catalysts.

Chiral Metal-Organic Framework Decorated with TEMPO Radicals for Sequential Oxidation/Asymmetric Cyanation Catalysis

A chiral porous metal-organic framework (MOF) decorated with radicals has been successfully constructed by cocrystallizing achiral (2,2,6,6-tetramethylpiperidin-1-yl)oxyl (TEMPO)-substituted tricarboxylate and enantiopure VO(salen)-derived dipyridine ligands. The chiral MOF can function as an efficient heterogeneous catalyst for the sequential alcohol oxidation/asymmetric cyanation of aldehyde reactions with enhanced activity and enantioselectivity compared to the homogeneous counterpart.

Multivariate Metal-Organic Frameworks as Multifunctional Heterogeneous Asymmetric Catalysts for Sequential Reactions

The search for versatile heterogeneous catalysts with multiple active sites for broad asymmetric transformations has long been of great interest, but it remains a formidable synthetic challenge. Here we demonstrate that multivariate metal-organic frameworks (MTV-MOFs) can be used as an excellent platform to engineer heterogeneous catalysts featuring multiple and cooperative active sites. An isostructural series of 2-fold interpenetrated MTV-MOFs that contain up to three different chiral metallosalen catalysts was constructed and used as efficient and recyclable heterogeneous catalysts for a variety of asymmetric sequential alkene epoxidation/epoxide ring-opening reactions. Interpenetration of the frameworks brings metallosalen units adjacent to each other, allowing cooperative activation, which results in improved efficiency and enantioselectivity over the sum of the individual parts. The fact that manipulation of molecular catalysts in MTV-MOFs can control the activities and selectivities would facilitate the design of novel multifunctional materials for enantioselective processes.

The first porphyrin-salen based chiral metal-organic framework for asymmetric cyanosilylation of aldehydes

The first porphyrin-salen based chiral metal-organic framework (ps-CMOF) constructed by judiciously incorporating metalloporphyrin and metallosalen struts into one MOF structure is reported, which can serve as an effective heterogeneous catalyst for the a

Chiral Covalent Organic Frameworks with High Chemical Stability for Heterogeneous Asymmetric Catalysis

Covalent organic frameworks (COFs) featuring chirality, stability, and function are of both fundamental and practical interest, but are yet challenging to achieve. Here we reported the metal-directed synthesis of two chiral COFs (CCOFs) by imine-condensat

A homochiral vanadium-salen based cadmium bpdc MOF with permanent porosity as an asymmetric catalyst in solvent-free cyanosilylation

A homochiral vanadium-salen based MOF with the pcu topology is constructed via in situ synthesis under solvothermal conditions. The synthesized MOF exhibits BET surface areas of 574 m2 g-1, showing the highest H2 adsorptio

Enantioselective Cyanosilylation of Ketones with Lithium(I) Dicyanotrimethylsilicate(IV) Catalyzed by a Chiral Lithium(I) Phosphoryl Phenoxide

A highly enantioselective cyanosilylation of ketones was developed by using a chiral lithium(I) phosphoryl phenoxide aqua complex as an acid/base cooperative catalyst. The pentacoordinate silicate generated in situ from Me3SiCN/LiCN acts as an extremely reactive cyano reagent. Described is a 30 gram scale reaction and the synthesis of the key precursor to (+)-13-hydroxyisocyclocelabenzine.

Enantioselective cyanosilylation of aldehydes catalyzed by a multistereogenic salen-Mn(III) complex with a rotatable benzylic group as a helping hand

A multistereogenic salen-Mn(iii) complex bearing an aromatic pocket and two benzylic groups as helping hands was found to be efficient in the catalysis of asymmetric cyanosilylation. The salen-Mn catalyst partially mimics the functions of biocatalysts by

Direct and Post-Synthesis Incorporation of Chiral Metallosalen Catalysts into Metal-Organic Frameworks for Asymmetric Organic Transformations

Two chiral porous metal-organic frameworks (MOFs) were constructed from [VO(salen)]-derived dicarboxylate and dipyridine bridging ligands. After oxidation of VIV to VV, they were found to be highly effective, recyclable, and reusable