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Upstream product

• 3481-02-5 cyclopropyl phenyl ketone 
• 1667-00-1 benzylcyclopropane 
• 1007-03-0 1-phenyl-1-cyclopropylmethanol 
• 98-88-4 benzoyl chloride 
• 108-05-4 vinyl acetate 
• 20525-76-2 dicyclopropylzinc 
• 100-52-7 benzaldehyde 

Relevant academic research and scientific papers

Chiral [RuCl2(dipyridylphosphane)(1,2-diamine)] catalysts: Applications in asymmetric hydrogenation of a wide range of simple ketones

The dipyridylphosphane/diamine - Ru complex combined with tBuOK in 2-propanol acts as a very effective catalyst system for the enantioselective hydrogenation of a diverse range of simple ketones including heteroaromatic ketones, substituted benzophenones, alkenyl ketones, and cyclopropyl ketones. The combination of desirable features, such as quantitative chemical yields within hours, broad substrate scope, excellent enantioselectivities (up to 99%), and high substrate-to-catalyst ratios, among others, makes the present catalyst system of high practical interest.

Tridentate nitrogen phosphine ligand containing arylamine NH as well as preparation method and application thereof

The invention discloses a tridentate nitrogen phosphine ligand containing arylamine NH as well as a preparation method and application thereof, and belongs to the technical field of organic synthesis. The tridentate nitrogen phosphine ligand disclosed by the invention is the first case of tridentate nitrogen phosphine ligand containing not only a quinoline amine structure but also chiral ferrocene at present, a noble metal complex of the type of ligand shows good selectivity and extremely high catalytic activity in an asymmetric hydrogenation reaction, meanwhile, a cheap metal complex of the ligand can also show good selectivity and catalytic activity in the asymmetric hydrogenation reaction, and is very easy to modify in the aspects of electronic effect and space structure, so that the ligand has huge potential application value. A catalyst formed by the ligand and a transition metal complex can be used for catalyzing various reactions, can be used for synthesizing various drugs, and has important industrial application value.

Visible-Light-Driven Catalytic Deracemization of Secondary Alcohols

Deracemization of racemic chiral compounds is an attractive approach in asymmetric synthesis, but its development has been hindered by energetic and kinetic challenges. Here we describe a catalytic deracemization method for secondary benzylic alcohols which are important synthetic intermediates and end products for many industries. Driven by visible light only, this method is based on sequential photochemical dehydrogenation followed by enantioselective thermal hydrogenation. The combination of a heterogeneous dehydrogenation photocatalyst and a chiral molecular hydrogenation catalyst is essential to ensure two distinct pathways for the forward and reverse reactions. These reactions convert a large number of racemic aryl alkyl alcohols into their enantiomerically enriched forms in good yields and enantioselectivities.

Kinetic resolution of sterically hindered secondary alcohols catalyzed by aminophosphinite organocatalyst

Kinetic resolution of secondary alcohols by benzoylation using a phosphinite derivative of (1S,2R)-1-amino-2-indanol as the catalyst was investigated. The aminophosphinite catalyst is effective for the kinetic resolution of aryl cycloalkyl carbinols with a small number of examples for organocatalytic kinetic resolution to achieve resolution with s = up to 44. Although the benzoylation of phenylalkanols proceeded with a low selectivity, 1-arylalkanols bearing at least one substituent at the ortho position on the benzene ring or a branched alkyl group on the carbinol carbon were resolved with acceptable selectivity.

A Chiral Metal-Organic Material that Enables Enantiomeric Identification and Purification

We show that CMOM-3S, a previously unreported porous crystalline metal-organic material that exhibits intrinsic homochirality, serves as a general-purpose chiral crystalline sponge (CCS) and a chiral stationary phase (CSP) for gas chromatography (GC). The properties of CMOM-3S are enabled by nano-sized channels connected to adaptable molecular recognition sites that mimic enzyme-binding sites. Further, CMOM-3S is composed of inexpensive components, facile to prepare, and requires only trace amounts of analyte. When coupled with the thermal and hydrolytic stability of CMOM-3S, these features mean that a coated fused silica capillary column in which CMOM-3S serves as a CSP is both more versatile and more robust than three benchmark commercial columns. That the enantiomer with the longer GC retention time is consistently captured in CCS experiments enables CMOM-3S to serve as a powerful tool to enable both chiral purification and enantiomer identification.

Expanding substrate scope of lipase-catalyzed transesterification by the utilization of liquid carbon dioxide

Secondary alcohols having bulky substituents on both sides of the chiral center are often poor substrates for most lipases. Here we reported that substrate scopes of two of the most used lipases, Candida antarctica lipase B and Burkholderia cepacia lipase, were found to be expanded toward more bulky secondary alcohols such as 1-phenyl-1-dodecanol and 2-methyl-1-phenyl-1-propanol by simply using them in liquid carbon dioxide as a solvent. The effects of solvents, reaction pressure, and pre-treatment of the enzyme with liquid CO2on this acceleration phenomenon were also studied.

Bimetallic Catalysis: Asymmetric Transfer Hydrogenation of Sterically Hindered Ketones Catalyzed by Ruthenium and Potassium

An efficient protocol for the asymmetric reduction of sterically hindered ketones under transfer-hydrogenation conditions was developed. The corresponding chiral alcohols were obtained in good to excellent yields with enantiomeric excess values up to 99 %. The role of the cation associated with the base present in the reduction reaction was investigated. In contrast to previous studies on this catalyst system, potassium ions rather than lithium ions significantly enhanced the reaction outcome.

Iron catalyzed asymmetric hydrogenation of ketones

Chiral molecules, such as alcohols, are vital for the manufacturing of fine chemicals, pharmaceuticals, agrochemicals, fragrances, and novel materials. These molecules need to be produced in high yield and high optical purity and preferentially catalytically. Among all the asymmetric catalytic reactions, asymmetric hydrogenation with H2 (AH) is the most widely used in the industry. With few exceptions, these AH processes use catalysts based on the three critical metals, rhodium, ruthenium, and iridium. Herein we describe a simple, industrially viable iron catalyst that allows for the AH of ketones, a process currently dominated by ruthenium and rhodium catalysts. By combining a chiral, 22-membered macrocyclic ligand with the cheap, readily available Fe 3(CO)12, a wide variety of ketones have been hydrogenated under 50 bar H2 at 45-65 C, affording highly valuable chiral alcohols with enantioselectivities approaching or surpassing those obtained with the noble metal catalysts. In contrast to AH by most noble metal catalysts, the iron-catalyzed hydrogenation appears to be heterogeneous.

Solution-phase synthesis and evaluation of tetraproline chiral stationary phases

A protocol was developed for the solution-phase synthesis of multigram amounts of two 9-fluorenylmethoxycarbonyl (Fmoc)-protected tetraproline peptides. These tetraproline peptides were then attached to amino derivatized silica gel. The replacement of the Fmoc group with the trimethylacetyl group lead to two tetraproline chiral stationary phases (CSPs). A comparison of the chromatographic behavior of these two solution-phase-synthesized tetraproline CSPs with that prepared by stepwise solid-phase synthesis revealed that all three had similar chromatographic performance for resolving 53 model analytes. This suggests that the solution-phase synthesis of oligoprolines, which allows for the specific benefits of good batch reproducibility, selector homogeneity, and possibly low cost, is a feasible alternative to the solid-phase synthesis of oligoproline CSPs. Copyright

Catalytic enantioselective oxidation of aromatic hydrocarbons with D 4-symmetric chiral ruthenium porphyrin catalysts

The [RuII(D4-Por*)(CO)(MeOH)] (D 4-H2Por* = tetrakis[(1S,4R,5R,8S)-1,2,3,4,5,6,7,8- octahydro-1,4:5,8-dimethanoanthracen-9-yl]porphyrin) complex 1 is an effective catalyst for asymmetric hydroxylation of aromatic hydrocarbons with 2,6-dichloropyridine N-oxide (Cl2pyNO) as terminal oxidant. Up to 76% ee was achieved for the catalytic hydroxylation of 4-ethyltoluene, 1,1-diethylindan and benzylcyclopropane. Both electron-donating and -withdrawing substituents were found to accelerate the catalytic oxidation reaction, and a large primary H/D kinetic isotope effect (kH/kD = 11 at 298 K) was observed for the catalytic ethylbenzene-d10 oxidation. A mechanism involving rate-limiting hydrogen atom abstraction by reactive oxoruthenium species is postulated.