90970-80-2

Upstream product

• 4427-92-3 4-Phenyl-1,3-dioxolan-2-one 
• 25779-13-9 (S)-1-phenyl-1,2-ethanediol 
• 616-38-6 carbonic acid dimethyl ester 
• 609-02-9 methyl-malonic acid dimethylester 
• 204581-95-3 (S)-4-Phenyl-[1,3,2]dioxathiolane 2-oxide 
• 108-59-8 malonic acid dimethyl ester 
• 64-18-6 formic acid 
• 7257-94-5 1-phenyl-2-(p-tolylsulfonyloxy)ethanone 
• 40434-87-5 toluene-4-sulfonic acid 2-hydroxy-2-phenylethyl ester 
• 503-38-8 trichloromethyl chloroformate 
• 96-09-3 styrene oxide 
• 124-38-9 carbon dioxide 
• 20780-54-5 (S)-styrene oxide 
• 20780-53-4 (R)-Styrene oxide 

Downstream Products

• 56613-81-1 (S)-2-Amino-1-phenyl-1-ethanol 
• 56613-80-0 D-2-phenylglycinol 
• 124817-06-7 (S)-2-azido-1-phenylethanol 
• 126923-26-0 (R)-2-azido-2-phenylethan-1-ol 
• 25779-13-9 (S)-1-phenyl-1,2-ethanediol 

Relevant academic research and scientific papers

Construction of an Asymmetric Porphyrinic Zirconium Metal-Organic Framework through Ionic Postchiral Modification

Herein, one kind of neutral chiral zirconium metal-organic framework (Zr-MOF) was reported from the porphyrinic MOF (PMOF) family with a metallolinker (MnIII-porphyrin) as the achiral polytopic linker [free base tetrakis(4-carboxyphenyl)porphyrin] and chiral anions. Achiral Zr-MOF was chiralized through the exchange of primitive anions with new chiral organic anions (postsynthetic exchange). This chiral functional porphyrinic MOF (CPMOF) was characterized by several techniques such as powder X-ray diffraction, Fourier transform infrared spectroscopy, ultraviolet-visible spectroscopy, 1H NMR, energy-dispersive X-ray spectroscopy, scanning electron microscopy, and Brunauer-Emmett-Teller measurements. In the resulting structure, there are two active metal sites as Lewis acid centers (Zr and Mn) and chiral species as Br?nsted acid sites along with their cooperation as nucleophiles. This CPMOF shows considerable bimodal porosity with high surface area and stability. Additionally, its ability was investigated in asymmetric catalyses of prochiral substrates. Interactions between framework chiral species and prochiral substrates have large impacts on the catalytic ability and chirality induction. This chiral catalyst proceeded asymmetric epoxidation and CO2 fixation reactions at lower pressure with high enantioselectivity due to Lewis acids and chiral auxiliary nucleophiles without significant loss of activity up to the sixth step of consecutive cycles of reusability. Observations revealed that chiralization of Zr-MOF could happen by a succinct strategy that can be a convenient method to design chiral MOFs.

Synthesis and a Catalytic Study of Diastereomeric Cationic Chiral-at-Cobalt Complexes Based on (R, R)-1,2-Diphenylethylenediamine

Here we report the first synthesis of two diastereomeric cationic octahedral Co(III) complexes based on commercially available (R,R)-1,2-diphenylethylenediamine and salicylaldehyde. Both diastereoisomers with opposite chiralities at the metal center (Λ and Δconfigurations) were prepared. The new Co(III) complexes possessed both acidic hydrogen-bond donating (HBD) NH moieties and nucleophilic counteranions and operate as bifunctional chiral catalysts for the challenging kinetic resolution of terminal and disubstituted epoxides by the reaction with CO2 under mild conditions. The highest selectivity factor (s) of 2.8 for the trans-chalcone epoxide was achieved at low catalyst loading (2 mol %) in chlorobenzene, which is the best achieved result currently for this type of substrate.

Catalytic, Kinetic, and Mechanistic Insights into the Fixation of CO2 with Epoxides Catalyzed by Phenol-Functionalized Phosphonium Salts

A series of hydroxy-functionalized phosphonium salts were studied as bifunctional catalysts for the conversion of CO2 with epoxides under mild and solvent-free conditions. The reaction in the presence of a phenol-based phosphonium iodide proceeded via a first order rection kinetic with respect to the substrate. Notably, in contrast to the aliphatic analogue, the phenol-based catalyst showed no product inhibition. The temperature dependence of the reaction rate was investigated, and the activation energy for the model reaction was determined from an Arrhenius-plot (Ea=39.6 kJ mol?1). The substrate scope was also evaluated. Under the optimized reaction conditions, 20 terminal epoxides were converted at room temperature to the corresponding cyclic carbonates, which were isolated in yields up to 99 %. The reaction is easily scalable and was performed on a scale up to 50 g substrate. Moreover, this method was applied in the synthesis of the antitussive agent dropropizine starting from epichlorohydrin and phenylpiperazine. Furthermore, DFT calculations were performed to rationalize the mechanism and the high efficiency of the phenol-based phosphonium iodide catalyst. The calculation confirmed the activation of the epoxide via hydrogen bonding for the iodide salt, which facilitates the ring-opening step. Notably, the effective Gibbs energy barrier regarding this step is 97 kJ mol?1 for the bromide and 72 kJ mol?1 for the iodide salt, which explains the difference in activity.

Method for preparing cyclic carbonate by immobilizing CO2 under catalysis of organic boric acid

The invention discloses a synthesis method for synergistically catalyzing carbon dioxide immobilization through weak Lewis acid phenylboronic acid and tetrabutylammonium bromide. According to the method, CO2 is immobilized by epoxide, and a cyclic carbonate product is generated. The method comprises the following step: under the concerted catalysis of phenylboronic acid and tetrabutylammonium bromide, performing reaction on epoxide as shown in a formula IV, a formula V or a formula VI and carbon dioxide to respectively obtain a cyclic carbonate product as shown in a formula I, a formula II or a formula III. According to the method, raw materials are convenient and easy to obtain, reaction conditions are mild, operation is easy and convenient, and the yield can reach 97%.

Synthesis of Ionic Liquids as Novel Nanocatalysts for Fixation of Carbon Dioxide with Epoxides by Using a Carbon Dioxide Balloon

Abstract: In the present study, the nanocatalyst of imidazolium based ionic liquids (ILs) is synthesized for the fixation of carbon dioxide (CO2) under moderate conditions by utilizing a balloon of CO2 with commercially available epoxides. IL incorporated porous dendritic fibrous nanosilica (DFNS) catalyst (IL/DFNS) was designed and synthesized. The synthesized catalyst was characterized using N2 absorption desorption isotherm, XPS, SEM, EDX, TGA, HR-TEM, and AFM. For cyclic carbonate, an environmental friendly catalyst of porous IL/DFNS indicate highly impressive catalytic efficiency from CO2 through CO2 fixation and epoxides under mild condition. Attendance of polar hydroxyl and anion exchange nature groups of IL frame work to high surface area is known as the main aspect to be reliable for elevated catalytic efficiency and also advance in stability of catalyst and providing a proper recyclability. Graphic Abstract: [Figure not available: see fulltext.].

Highly regio- And stereoselective synthesis of cyclic carbonates from biomass-derived polyols: Via organocatalytic cascade reaction

The cascade reaction of CO2, vicinal diols, and propargylic alcohol, was firstly achieved by dual Lewis base (LB) organocatalytic systems involving LB-CO2 adducts and commercially available organic amines. This methodology could overcome the chemical inertness of CO2, providing an alternative route to various functionalized five-membered cyclic carbonates in moderate to high yields under mild reaction conditions (25 °C, 1.0 atm of CO2). More importantly, this method could also be applied for facile and efficient synthesis of chiral polycyclic carbonates from biomass-derived polyols with complete configuration retention of chiral centers. This study provides an environment-friendly, scalable and cost effective protocol to construct value-added cyclic carbonates with multi-functional groups and chiral centers.

Chiral Bifunctional Metalloporphyrin Catalysts for Kinetic Resolution of Epoxides with Carbon Dioxide

Chiral binaphthyl-strapped Zn(II) porphyrins with triazolium halide units were synthesized as bifunctional catalysts for kinetic resolution of epoxides with CO2. Several catalysts were screened by changing the linker length and nucleophilic counteranions, and the optimized catalyst accelerated the enantioselective reaction at ambient temperature to produce optically active cyclic carbonates and epoxides.

Kinetic Resolution of Epoxides with CO2 Catalyzed by a Chiral-at-Iridium Complex

Chiral-at-metal bis-cyclometalated iridium(III) complexes are introduced as a new class of chiral catalysts for the reaction of epoxides with CO2 to form cyclic carbonates under conditions of kinetic resolution. Reactions are typically performed at room temperature in the presence of 1 mol % of iridium catalyst and 1.5 mol % of tetraethylammonium bromide as the nucleophilic cocatalyst to provide selectivity factors of up to 16.6. A variety of monosubstituted epoxides, including styrene epoxide, epoxides with aliphatic side chains, glycidyl ethers, and a glycidyl ester, are found to be suitable substrates. No polymerization side reaction is observed for any of the investigated substrates.

Bifunctional phase-transfer catalysts for fixation of CO2 with epoxides under ambient pressure

A series of bifunctional phase-transfer catalysts with a quaternary onium center and a hydrogen-bonding donor group were prepared for the fixation of CO2 with commercially available epoxides under mild conditions by using a CO2 balloon (1 atm). In the presence of 2.5 mol% of achiral bifunctional phase-transfer catalysts, cyclic carbonates were obtained in good to excellent yields (up to 95%). Additionally, optical carbonates and epoxides were obtained through the kinetic resolution of rac-epoxides by 1 mol% of chiral bifunctional phase-transfer catalysts with low enantioselectivities. These catalysts featured a simple synthetic route, good modularity and high efficiency.

A novel homochiral metal-organic framework with an expanded open cage based on (: R)-3,3′-bis(6-carboxy-2-naphthyl)-2,2′-dihydroxy-1,1′-binaphthyl: synthesis, X-ray structure and efficient HPLC enantiomer separation

A new homochiral metal-organic framework (MOF) with an expanded open cage based on the (R)-3,3′-bis(6-carboxy-2-naphthyl)-2,2′-dihydroxy-1,1′-binaphthyl ligand was synthesized and utilized as a novel chiral stationary phase for high-performance liquid chromatography. Twelve racemates including sec-alcohols, sulfoxides, epoxides, lactone, 1,3-dioxolan-2-one, and oxazolidinone were used as analytes for evaluating the separation properties of the chiral-MOF-packed column. Experimentally, the homochiral MOF offered good molecular recognition ability, which suggests good prospects for the application of chiral MOFs as stationary phases for enantioseparation.