129097-94-5

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 
• 124-38-9 carbon dioxide 
• 20780-54-5 (S)-styrene oxide 
• 96-09-3 styrene oxide 
• 2211-95-2 1-(3-chlorophenoxy)-2,3,epoxypropane 
• 115-19-5 2-methyl-but-3-yn-2-ol 

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

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.

THE RESOLUTION OF RACEMIC 1,2-DIOLS BY THE ESTERASE CATALYSED HYDROLYSIS OF THE CORRESPONDING CYCLIC CARBONATE

Racemic 1-phenyl-1,2-ethane diol can be resolved by the pig liver esterase catalysed hydrolysis of the corresponding cyclic carbonate to give the (R) and (S) 1-phenyl-1,2-ethane diol with an ee of 97 and 78percent respectively. Key Words: diol resolution, pig liver esterase

Covalent organic frameworks: Efficient, metal-free, heterogeneous organocatalysts for chemical fixation of CO2 under mild conditions

The cycloaddition of CO2 to epoxides to form cyclic carbonates is very promising and does not generate any side products. Metal-free, heterogeneous organocatalysts offer an environmentally friendly alternative to traditional metal-based catalysts. Herein two triazine-based covalent organic frameworks (COF-JLU6 and COF-JLU7) were successfully synthesized under solvothermal conditions. The structural and chemical properties of COFs were fully characterized by using powder X-ray diffraction analysis, structural simulation, Fourier transform infrared spectroscopy, 13C solid-state NMR spectroscopy, electron microscopy, thermogravimetric analysis and nitrogen adsorption. The two COF materials combine mesopores, high crystallinity and good stability, as well as a large number of hydroxy groups in the pore walls. They possess a high Brunauer-Emmett-Teller (BET) specific surface area up to 1390 m2 g-1 and a large pore volume of 1.78 cm3 g-1. The COF-JLU7 displays a high CO2 uptake of 151 mg g-1 at 273 K and 1 bar. Importantly, COF-JLU7 was found to be a highly effective catalyst to convert CO2 into cyclic carbonate through the cycloaddition reaction with epoxides under mild conditions. The effect of reaction parameters, such as reaction temperature, reaction time and CO2 pressure, on the catalytic performance was also investigated in detail. Moreover, the new framework-based catalyst can be recovered and reused five times without a significant loss of catalytic efficiency.

Highly enantioselective hydrolysis of phenyl-1,2-ethanediol cyclic carbonates by newly isolated Bacillus sp. ECU0015

A bacterial strain (No. ECU0015), which catalyzes the hydrolysis of phenyl-1,2-ethanediol cyclic carbonates (4-phenyl-1,3-dioxolan-2-one, 1) to (S)-1-phenyl-1,2-ethanediol (2) with high enantioselectivity, was newly isolated from soil samples utilizing the cyclic carbonate as sole carbon and energy source. The bacterium was later identified as Bacillus species by its 16S rDNA sequence and phylogenetic analysis. The optimal reaction temperature and pH for the asymmetric hydrolysis of 1 using whole cells were 35 °C and pH 7.3, respectively. Partial bio-oxidation of the produced (R)-diol was observed, resulting in an increase in the eep (enantiomeric excess of product) of the main product (S)-diol. Under the improved reaction condition, the target product (S)-diol was prepared in gram scale, affording an excellent ee p (>99%) with a moderate yield (27.8%) as compared to the maximum theoretical yield of 50% for kinetic resolution. This strain of Bacillus sp. also displayed fairly good activity and enantioselectivity towards some other compounds tested, such as 2-acetoxy-2-phenylacetic acid (3) and its derivatives.

Pushing the Limits with Squaramide-Based Organocatalysts in Cyclic Carbonate Synthesis

Squaramides are presented as modular, easy to optimize, and effective catalysts for the conversion of epoxides and carbon dioxide into cyclic organic carbonates (COCs). The catalytic potential of these squaramides, in combination with a suitable halide nucleophile, is particularly noted when internal epoxides are examined as substrates, and their transformation into disubstituted COCs marks a rare case of an effective organocatalyst for these challenging conversions. Control experiments support the mechanistic view that the squaramides are predominantly involved in the stabilization of intermediate oxo and carbonato anions which, after their formation, are able to displace a bromide nucleophile from an initially formed 1:1 assembly comprising the squaramide host.

Quaternary ammonium hydroxide as a metal-free and halogen-free catalyst for the synthesis of cyclic carbonates from epoxides and carbon dioxide

Tetrabutylammonium hydroxide (TBAH) and other quaternary ammonium hydroxides catalyzed the cycloaddition of CO2 to epoxides under solvent-free conditions to give cyclic carbonates. When TBAH was exposed to CO2, TBAH was converted into tetrabutylammonium bicarbonate (TBABC), which was a catalytically active species. A D-labeled epoxide and an optically active epoxide were used to study the reaction mechanism, which invoked three plausible pathways. Among them, path A seemed to be predominant; the bicarbonate ion of TBABC attacks the less hindered C atom of the epoxide to generate a ring-opened alkoxide intermediate, which adds to CO2 to give a carbonate ion, and the subsequent cyclization yields a cyclic carbonate. Density functional theory (DFT) calculations successfully delineated the potential energy profile for each reaction pathway, among which path A was the lowest-energy pathway in accordance with the experimental results. The tetrabutylammonium (TBA) cation carries the positive charges on the H atoms, but not on the central N atom, and the positively charged H atoms close to the central N atom form an anion-binding site capable of stabilizing various anionic transition states and intermediates.

Metal-Organic Polymers Containing Discrete Single-Walled Nanotube as a Heterogeneous Catalyst for the Cycloaddition of Carbon Dioxide to Epoxides

The cycloaddition of carbon dioxide to epoxides to produce cyclic carbonates is quite promising and does not result in any side products. A discrete single-walled metal-organic nanotube was synthesized by incorporating a tetraphenyl-ethylene moiety as the four-point connected node. The assembled complex has a large cross-section, with an exterior wall diameter of 3.6 nm and an interior channel diameter of 2.1 nm. It features excellent activity toward the cycloaddition of carbon dioxide, with a turnover number of 17,500 per mole of catalyst and an initial turnover frequency as high as 1000 per mole of catalyst per hour. Only minimal decreases in the catalytic activity were observed after 70 h under identical reaction conditions, and a total turnover number as high as 35,000 was achieved. A simple comparison of relative porous MOFs suggested that the cross-section of the channels is an important factor influencing the transport of the substrates and products through the channel.

Synthesis of cyclic carbonates from CO2 and epoxides catalyzed by low loadings of benzyl bromide/DMF at ambient pressure

An efficient, metal-free catalytic system for the conversion of CO2 and epoxides to cyclic carbonates under mild conditions with good-to-excellent yields (57-99%) was developed. A possible reaction mechanism involving the electrophilic activation of epoxides by benzyl cations and nucleophilic activation of CO2 by DMF is proposed. This journal is

Chiroptical and catalytic properties of doubly binaphthyl-strapped chiral porphyrins

Doubly (R)-binaphthyl-strapped porphyrins with methylene chains were synthesized. The CD spectra showed the positive Cotton effect around the Soret bands, and several porphyrins showed CPL. In addition, we found that the chiral porphyrins were applicable to kinetic resolution of epoxide with CO2.

Rhodium versus ruthenium: Contrasting behaviour in the asymmetric transfer hydrogenation of α-substituted acetophenones

The reduction of a number of α-substituted acetophenones has been achieved using both ruthenium(II)- and rhodium(III)-based asymmetric transfer hydrogenation catalysts employing formic acid as the hydrogen donor.