30182-12-8

Upstream product

• 6705-50-6 7-oxa-bicyclo[2.2.1]hept-2Z-ene 
• 6671-70-1 2,3-dioxabicyclo[2,2,2]oct-5-ene 
• 67-63-0 isopropyl alcohol 
• 53762-85-9 (1S,4R)-Cyclohex-2-ene-1,4-diol 
• 100-66-3 methoxybenzene 
• 2886-59-1 1-methoxycyclohexa-1,4-diene 
• 6671-70-1 (1R,1S)-2,3-dioxabicyclo[2.2.2]oct-5-ene 
• 822-66-2 3-cyclohexen-1-ol 
• 1021418-48-3 8-hydroxy-1,4-dioxa-spiro[4,5]dec-6-ene 
• 1165952-91-9 cyclohexa-1,3-diene 
• 930-68-7 cyclohexenone 
• 4683-24-3 1,4-dioxa-spiro[4.5]dec-6-en-8-one 
• 110-83-8 cyclohexene 
• 556-48-9 1,4-Cyclohexanediol 

Downstream Products

• 97856-74-1 2-(4-Chloro-phenyl)-tetrahydro-benzo[1,3]dioxol-5-one 
• 97856-73-0 2-Methyl-5-oxohexahydro-1,3-benzodioxole 
• 119414-47-0 (+/-)-4-(tert-butyl(dimethyl)silyloxy)-2-cyclohexen-1-one 
• 1026935-73-8 4-(1-methoxy-cyclohexyloxy)-cyclohex-2-enone 
• 132746-89-5 (+)-(R)-4-hydroxycyclohex-2-enone 
• 119478-74-9 (S)-4-((tert-butyldimethylsilyl)oxy)cyclohex-2-enone 
• 164577-42-8 <(4R)-(+)-tert-Butoxydimethylsiloxy>-2-cyclohexen-1-on 
• 794526-34-4 (3R,4S)-3-benzylthio-4-hydroxycyclohexan-1-one 
• 794526-36-6 Acetic acid (1R,2S)-2-benzylsulfanyl-4-oxo-cyclohexyl ester 
• 121652-00-4 (S)-(-)-4-hydroxy-2-cyclohexan-1-one 
• 132658-89-0 (R)-4-acetoxy-2-cyclohexen-1-one 

Relevant academic research and scientific papers

THERMAL AND PHOTOCHEMICAL REACTIONS OF UNSATURATED BICYCLIC ENDOPEROXIDES

Thermal, and especially photochemical, rearrangement of the endoperoxides (1) and (5)-(11) gives βγ-epoxycycloalkanones as primary products, accompanied by the expected syn-diepoxides.

Enantioselective synthesis of γ-hydroxyenones by chiral base-catalyzed Kornblum DeLaMare rearrangement

A cinchona-alkaloid catalyzed asymmetric Kornblum DeLaMare rearrangement has been developed. Thus, enantioenriched 4-hydroxyenones are prepared from dienes by a two-step sequence involving photochemical dioxygenation and chiral base-catalyzed desymmetriza

The total synthesis of the fungal metabolite diversonol

(Chemical Equation Presented) Mission accomplished. The fungal metabolite diversonol has been synthesized for the first time. A key step in the total synthesis was the domino oxa-Michael-aldol condensation of salicylic aldehyde 1 and 4-hydroxycyclohexenon

Synthesis of oxazole analogs of streptolidine lactam

The streptolidine lactam is an amino acid constituent of streptothricin antibiotics, which inhibit protein synthesis by targeting the bacterial ribosome but suffer from toxicity as a result of the basicity of the aminoimidazole scaffold in the natural products. On the basis of the streptolidine structure, we designed and synthesized oxazole analogs with six- and seven-membered lactam rings as building blocks for RNA-targeted ligands. These analogs benefit from a dense network of hydrogen-bond donors and acceptors within a rigid nonplanar heterocyclic system that has attenuated basicity. Oxazole analogs based on the streptolidine scaffold of natural RNA-binding streptothricin antibiotics were designed and synthesized as building blocks for RNA-targeted ligands. These synthetic analogs with six- and seven-membered lactam rings benefit from a dense network of hydrogen-bond donors and acceptors within a rigid nonplanar heterocyclic system that has attenuated basicity. Copyright

Activation of H2O2over Zr(IV). Insights from Model Studies on Zr-Monosubstituted Lindqvist Tungstates

Zr-monosubstituted Lindqvist-type polyoxometalates (Zr-POMs), (Bu4N)2[W5O18Zr(H2O)3] (1) and (Bu4N)6[{W5O18Zr(μ-OH)}2] (2), have been employed as molecular models to unravel the mechanism of hydrogen peroxide activation over Zr(IV) sites. Compounds 1 and 2 are hydrolytically stable and catalyze the epoxidation of C?C bonds in unfunctionalized alkenes and α,β-unsaturated ketones, as well as sulfoxidation of thioethers. Monomer 1 is more active than dimer 2. Acid additives greatly accelerate the oxygenation reactions and increase oxidant utilization efficiency up to >99%. Product distributions are indicative of a heterolytic oxygen transfer mechanism that involves electrophilic oxidizing species formed upon the interaction of Zr-POM and H2O2. The interaction of 1 and 2 with H2O2 and the resulting peroxo derivatives have been investigated by UV-vis, FTIR, Raman spectroscopy, HR-ESI-MS, and combined HPLC-ICP-atomic emission spectroscopy techniques. The interaction between an 17O-enriched dimer, (Bu4N)6[{W5O18Zr(μ-OCH3)}2] (2′), and H2O2 was also analyzed by 17O NMR spectroscopy. Combining these experimental studies with DFT calculations suggested the existence of dimeric peroxo species [(μ-?2:?2-O2){ZrW5O18}2]6- as well as monomeric Zr-hydroperoxo [W5O18Zr(?2-OOH)]3- and Zr-peroxo [HW5O18Zr(?2-O2)]3- species. Reactivity studies revealed that the dimeric peroxo is inert toward alkenes but is able to transfer oxygen atoms to thioethers, while the monomeric peroxo intermediate is capable of epoxidizing C?C bonds. DFT analysis of the reaction mechanism identifies the monomeric Zr-hydroperoxo intermediate as the real epoxidizing species and the corresponding α-oxygen transfer to the substrate as the rate-determining step. The calculations also showed that protonation of Zr-POM significantly reduces the free-energy barrier of the key oxygen-transfer step because of the greater electrophilicity of the catalyst and that dimeric species hampers the approach of alkene substrates due to steric repulsions reducing its reactivity. The improved performance of the Zr(IV) catalyst relative to Ti(IV) and Nb(V) catalysts is respectively due to a flexible coordination environment and a low tendency to form energy deep-well and low-reactive Zr-peroxo intermediates.

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.

Discovery and Optimization of DNA Gyrase and Topoisomerase IV Inhibitors with Potent Activity against Fluoroquinolone-Resistant Gram-Positive Bacteria

Herein, we describe the discovery and optimization of a novel series that inhibits bacterial DNA gyrase and topoisomerase IV via binding to, and stabilization of, DNA cleavage complexes. Optimization of this series led to the identification of compound 25

Heterogeneous epoxidation of menadione with hydrogen peroxide over the zeolite imidazolate framework ZIF-8

The zeolite imidazolate framework ZIF-8 exhibits superior catalytic performance in the epoxidation of the electron-deficient CC bond in menadione using aqueous hydrogen peroxide as the oxidant. The catalysis has a truly heterogeneous nature and the framework structure remains intact. This is the first example of oxidation catalysis with ZIF-8.

Nucleophilic versus Electrophilic Activation of Hydrogen Peroxide over Zr-Based Metal-Organic Frameworks

Zr-based metal-organic frameworks (Zr-MOF) UiO-66 and UiO-67 catalyze thioether oxidation in nonprotic solvents with unprecedentedly high selectivity toward corresponding sulfones (96-99% at ca. 50% sulfide conversion with only 1 equiv of H2O2). The reaction mechanism has been investigated using test substrates, kinetic, adsorption, isotopic (18O) labeling, and spectroscopic tools. The following facts point out a nucleophilic character of the peroxo species responsible for the superior formation of sulfones: (1) nucleophilic parameter XNu = 0.92 in the oxidation of thianthrene 5-oxide and its decrease upon addition of acid; (2) sulfone to sulfoxide ratio of 24 in the competitive oxidation of methyl phenyl sulfoxide and p-Br-methyl phenyl sulfide; (3) significantly lower initial rates of methyl phenyl sulfide oxidation relative to methyl phenyl sulfoxide (kS/kSO = 0.05); and (4) positive slope ρ = +0.42 of the Hammett plot for competitive oxidation of p-substituted aryl methyl sulfoxides. Nucleophilic activation of H2O2 on Zr-MOF is also manifested by their capability of catalyzing epoxidation of electron-deficient C═C bonds in α,β-unsaturated ketones accompanied by oxidation of acetonitrile solvent. Kinetic modeling on methyl phenyl sulfoxide oxidation coupled with adsorption studies supports a mechanism that involves the interaction of H2O2 with Zr sites with the formation of a nucleophilic oxidizing species and release of water followed by oxygen atom transfer from the nucleophilic oxidant to sulfoxide that competes with water for Zr sites. The nucleophilic peroxo species coexists with an electrophilic one, ZrOOH, capable of oxygen atom transfer to nucleophilic sulfides. The predominance of nucleophilic activation of H2O2 over electrophilic one is, most likely, ensured by the presence of weak basic sites in Zr-MOFs identified by FTIR spectroscopy of adsorbed CDCl3 and quantified by adsorption of isobutyric acid.

Continuous Endoperoxidation of Conjugated Dienes and Subsequent Rearrangements Leading to C-H Oxidized Synthons

We have investigated the continuous flow photooxidation of several conjugated dienes and subsequent rearrangement using a practical and safe continuous-flow homemade engineered setup. End-to-end approaches involving endoperoxidation, Kornblum-DeLaMare rearrangement, and additional rearrangements are comprehensively detailed with optimization, scope, and scale-up to obtain useful hydroxyenones, furans, and 1,4-dicarbonyl building blocks.