65678-03-7

Upstream product

• 628-92-2 Cycloheptene 
• 563-63-3 silver(I) acetate 
• 7553-56-2 iodine 
• 1394206-49-5 2-((2,2,6,6-tetramethylpiperidin-1-yl)oxy)cycloheptanone 
• 502-42-1 cycloheptanone 
• 110162-59-9 cis-8,10-Dioxabicyclo<5.3.0>decan-9-one 
• 76519-87-4 (1R,7S)-cycloheptene oxide 
• 291-64-5 cycloheptane 
• 286-45-3 8-oxabicyclo[5.1.0]octane 
• 13553-19-0 trans-cycloheptane-1,2-diol 
• 7487-88-9 magnesium sulfate 
• 98-88-4 benzoyl chloride 
• 108-24-7 acetic anhydride 
• 64-19-7 acetic acid 

Downstream Products

• 111-16-0 heptanedioic acid 
• 71691-87-7 α-benzyloxycycloheptanone 
• 53185-69-6 pimelaldehyde 
• 1373965-43-5 2-methoxy-6,7,8,9-tetrahydro-5H-10-oxabenzo[a]azulene 
• 172292-09-0 [(1R,2R)-2-((E)-Styryl)-cyclohexyl]-acetic acid (1R,2R)-2-hydroxy-cycloheptyl ester 

Relevant academic research and scientific papers

Manipulating the stereoselectivity of limonene epoxide hydrolase by directed evolution based on iterative saturation mutagenesis

Limonene epoxide hydrolase from Rhodococcus erythropolis DCL 14 (LEH) is known to be an exceptional epoxide hydrolase (EH) because it has an unusual secondary structure and catalyzes the hydrolysis of epoxides by a rare one-step mechanism in contrast to the usual two-step sequence. From a synthetic organic viewpoint it is unfortunate that LEH shows acceptable stereoselectivity essentially only in the hydrolysis of the natural substrate limonene epoxide, which means that this EH cannot be exploited as a catalyst in asymmetric transformations of other substrates. In the present study, directed evolution using iterative saturation mutagenesis (ISM) has been tested as a means to engineer LEH mutants showing broad substrate scope with high stereoselectivity. By grouping individual residues aligning the binding pocket correctly into randomization sites and performing saturation mutagenesis iteratively using a reduced amino acid alphabet, mutants were obtained which catalyze the desymmetrization of cyclopentene-oxide with stereoselective formation of either the (R,R)- or the (S,S)-diol on an optional basis. The mutants prove to be excellent catalysts for the desymmetrization of other meso-epoxides and for the hydrolytic kinetic resolution of racemic substrates, without performing new mutagenesis experiments. Since less than 5000 tranformants had to be screened for achieving these results, this study contributes to the generalization of ISM as a fast and reliable method for protein engineering. In order to explain some of the stereoselective consequences of the observed mutations, a simple model based on molecular dynamics simulations has been proposed.

Selective Isomerization via Transient Thermodynamic Control: Dynamic Epimerization of trans to cis Diols

Traditional approaches to stereoselective synthesis require high levels of enantio- and diastereocontrol in every step that forms a new stereocenter. Here, we report an alternative approach, in which the stereochemistry of organic substrates is selectivel

g-C3N4/metal halide perovskite composites as photocatalysts for singlet oxygen generation processes for the preparation of various oxidized synthons

g-C3N4/metal halide perovskite composites were prepared and used for the first time as photocatalysts forin situ1O2generation to perform hetero Diels-Alder, ene and oxidation reactions with suitable dienes and alkenes. The standardized methodology was made applicable to a variety of olefinic substrates. The scope of the method is finely illustrated and the reactions afforded desymmetrized hydroxy-ketone derivatives, unsaturated ketones and epoxides. Some limitations were also observed, especially in the case of the alkene oxidations, and poor chemoselectivity was somewhere observed in this work which is the first application of MHP-based composites forin situ1O2generation. The experimental protocol can be used as a platform to further expand the knowledge and applicability of MHPs to organic reactions, since perovskites offer a rich variety of tuning strategies which may be explored to improve reaction yields and selectivities.

Absolute configuration of trans-perhydroazulene

We present the absolute configuration (AC) determination of an alkane, trans-perhydroazulene (1), that displays the naturally very common trans fused [5,7] ring system. We outline the first synthesis yielding enantiopure 1 and the application of optical rotatory dispersion (ORD) and vibrational circular dichroism (VCD) techniques. The spectroscopic results are in excellent agreement with the computed ORD at B3LYP/6-311++G(2d,2p) and the computed VCD spectrum at B3LYP/6-311++G(d,p), providing an assignment of the AC as (R,R)-(+)-1.

Influence of the channel size of isostructural 3d-4f MOFs on the catalytic aerobic oxidation of cycloalkenes

The present work reports a new group of heterogeneous catalysts with a 3D structure, CuLnIDA, {[Cu3Ln2(IDA)6]·8H2O} (Ln: LaIII, GdIII or YbIII), with an organic linker (H2IDA: iminodiacetic acid). Different sets of O2 pressure and time were used in order to obtain the optimal reaction conditions at 75 °C. The reaction was found to depend on the [aldehyde]/[substrate] ratio. The best results, with a conversion of 73% for CuLaIDA as the catalyst, were obtained for the smallest ratio of 0.2. Finally, the importance of the pore size was analysed by comparing the catalytic activity of the as formed catalyst with that of the thermally activated one. The conversion increased ca. 26-35% for the different catalysts when they were previously activated. In addition, the selectivity increased towards cyclohexenone. The use of molecular oxygen as the oxidizing agent in a system where an auxiliary solvent is not used, as the cyclohexene substrate and products play the role of a solvent, permitted us to generate a more friendly environmental system for the oxidation of cycloalkenes under mild conditions.

Desymmetrization of meso-1,2-Diols by a Chiral N,N-4-Dimethylaminopyridine Derivative Containing a 1,1′-Binaphthyl Unit: Importance of the Hydroxy Groups

We developed an acylative desymmetrization of meso-1,2-diols using a binaphthyl-based N,N-4-dimethylaminopyridine (DMAP) derivative 1h with tert-alcohol substituents. The reaction proceeds with a wide range of acyclic meso-1,2-diols and six-membered-ring meso-1,2-diols to provide a monoacylate selectively with a high enantiomeric ratio (er). Only 0.1 mol % of the catalyst facilitated the reaction within a short reaction time (3 h) to afford enantio-enriched monoacylated products in moderate to good yield. Several control experiments revealed that the tert-alcohol units of catalyst 1h play a significant role in achieving high catalytic activity, chemoselectivity of monoacylation, and enantioselectivity.

Hydrogen Bonding-Assisted Enhancement of the Reaction Rate and Selectivity in the Kinetic Resolution of d,l-1,2-Diols with Chiral Nucleophilic Catalysts

An extremely efficient acylative kinetic resolution of d,l-1,2-diols in the presence of only 0.5 mol% of binaphthyl-based chiral N,N-4-dimethylaminopyridine was developed (selectivity factor of up to 180). Several key experiments revealed that hydrogen bonding between the tert-alcohol unit(s) of the catalyst and the 1,2-diol unit of the substrate is critical for accelerating the rate of monoacylation and achieving high enantioselectivity. This catalytic system can be applied to a wide range of substrates involving racemic acyclic and cyclic 1,2-diols with high selectivity factors. The kinetic resolution of d,l-hydrobenzoin and trans-1,2-cyclohexanediol on a multigram scale (10 g) also proceeded with high selectivity and under moderate reaction conditions: (i) very low catalyst loading (0.1 mol%); (ii) an easily achievable low reaction temperature (0 °C); (iii) high substrate concentration (1.0 M); and (iv) short reaction time (30 min). (Figure presented.).

PYRAZOLOPYRIMIDINE INHIBITORS OF IRAK4 ACTIVITY

The present invention relates to pyrazolopyrimidine inhibitors of IRAK4 of formula (I) and provides compositions comprising such inhibitors, as well as methods therewith for treating IRAK4-mediated or -associated conditions or diseases.

Selective transition-metal-free vicinal cis-dihydroxylation of saturated hydrocarbons

A transition-metal-free cis-dihydroxylation of saturated hydrocarbons under ambient reaction conditions has been developed. The described approach allows a direct and selective synthesis of vicinal diols. The new reaction thereby proceeds via radical iodination and a sequence of oxidation steps. A broad scope of one-pot dual C(sp3)-H bond functionalization for the selective synthesis of vicinal syn-diols was demonstrated.

Chiral-Substituted Poly-N-vinylpyrrolidinones and Bimetallic Nanoclusters in Catalytic Asymmetric Oxidation Reactions

A new class of poly-N-vinylpyrrolidinones containing an asymmetric center at C5 of the pyrrolidinone ring were synthesized from l-amino acids. The polymers, particularly 17, were used to stabilize nanoclusters such as Pd/Au for the catalytic asymmetric oxidations of 1,3- and 1,2-cycloalkanediols and alkenes, and Cu/Au was used for C-H oxidation of cycloalkanes. It was found that the bulkier the C5 substituent in the pyrrolidinone ring, the greater the optical yields produced. Both oxidative kinetic resolution of (±)-1,3- and 1,2-trans-cycloalkanediols and desymmetrization of meso cis-diols took place with 0.15 mol % Pd/Au (3:1)-17 under oxygen atmosphere in water to give excellent chemical and optical yields of (S)-hydroxy ketones. Various alkenes were oxidized with 0.5 mol % Pd/Au (3:1)-17 under 30 psi of oxygen in water to give the dihydroxylated products in >93% ee. Oxidation of (R)-limonene at 25 °C occurred at the C-1,2-cyclic alkene function yielding (1S,2R,4R)-dihydroxylimonene 49 in 92% yield. Importantly, cycloalkanes were oxidized with 1 mol % Cu/Au (3:1)-17 and 30% H2O2 in acetonitrile to afford chiral ketones in very good to excellent chemical and optical yields. Alkene function was not oxidized under the reaction conditions. Mechanisms were proposed for the oxidation reactions, and observed stereo- and regio-chemistry were summarized.