34877-64-0

Upstream product

• 5439-43-0 3-phenyl-1,4-dioxaspiro<4,5>decan-2-one 
• 908094-04-2 phenyldiazomethane 
• 108-94-1 cyclohexanone 
• 618-31-5 benzylidene dibromide 
• 831-91-4 Benzyl phenyl sulfide 
• 42711-88-6 S-benzyltetrahydrothiophenium chloride 
• 945-49-3 cyclohexylphenylmethanol 
• 1666-17-7 (E)-N′-benzylidene-4-methylbenzenesulfonohydrazide 
• 1608-31-7 (cyclohexylidenemethyl)benzene 
• 98-87-3 benzylidene dichloride 

Downstream Products

• 14996-78-2 2-phenylcycloheptanone 
• 22612-69-7 1-phenylcyclohexane-1-carbaldehyde 
• 712-50-5 Cyclohexyl phenyl ketone 
• 947-19-3 1-hydroxycyclohexyl phenyl ketone 
• 1135-72-4 1-(hydroxy(phenyl)methyl)cyclohexan-1-ol 

Relevant academic research and scientific papers

Domino Processes of Arynes Reacting with Three Classes of Nucleophiles for Organic Syntheses

Synthetic application of arynes is broadened by their reactions with neutral N-, S-, and O-containing nucleophiles to produce three types of compounds. Accordingly, 1,2-dihydroquinolines are synthesized from Schiff bases, alkynes, and arynes through a Diels-Alder reaction. Epoxides are prepared from thioethers and arynes along with aldehydes or ketones through a Johnson-Corey-Chaykovsky reaction. Phenolic ethers are produced from allyl ethers and arynes through a Claisen-type rearrangement. These target molecules, including natural products γ-asarone, asaricin, and a cholesteryl phenolic ether, are formed through reactions initiated by arynes. These new reactions share a prevailing feature of domino processes, which are carried out in a single flask and afford the desired products in good to high yields.

Synthesis of α-Arylated Cycloalkanones from Congested Trisubstituted Spiro-epoxides: Application of the House-Meinwald Rearrangement for Ring Expansion

A three-step sequence for the synthesis of α-arylated cyclohexanones and the most challenging cycloheptanones is reported. First, an efficient one-pot synthesis of β,β'-disubstituted benzylidene cycloalkanes (styrenes) using the palladium-catalyzed Barluenga reaction from readily available feedstock chemicals is described. Furthermore, an epoxidation followed by the House-Meinwald rearrangement (HMR) of spiro-epoxides is reported to produce a number of α-arylated cycloalkanones upon ring expansion. Reactions catalyzed by bismuth triflate underwent quasi-exclusively ring expansion for all substrates (electronically poor and rich), with yields ranging from 15% to 95%, thus demonstrating the difficulty of achieving ring enlargement for electron-deficient spiro-epoxides. On the other hand, by means of catalysis with aluminum trichloride, the rearrangement of spiro-epoxides proceeded typically in high yields and with remarkable regioselectivity on a broader substrate scope. In this case, a switch of regioselectivity was achieved for spiro-epoxides with electron-withdrawing substituents which enable the method to be successfully extended to some chemospecific arene shifts and the synthesis of aldehydes bearing a α-quaternary carbon. While the HMR has been extensively studied for smaller ring enlargement, we are pleased to report herein that larger cyclohexanones and cycloheptanones can be obtained efficiently from more sterically demanding trisubstituted spiro-epoxides bearing electron-releasing and electron-neutral arene substituents.

Formation of epoxides and N-arylaziridines via a simple Mg-Barbier reaction in DMF

The Mg-activation of benzal bromide 2b in DMF in the presence of carbonyl compounds 1 or imines 4 leads to epoxides 3 and N-arylaziridines 5, respectively, with acceptable isolated yields. It was found that DMF is likely involved in this process to form a nucleophilic intermediate by reaction with a first generated electrophilic carbene. Results obtained in this chemical approach are compared to those obtained using electrochemical activation, also in DMF.

An effective dual copper-and sulfide-catalytic system for the epoxidation of aldehydes with phenyldiazomethane

Epoxides have been obtained from alde-hydes and phenyldiazomethane using catalytic amounts of both the copper homoscorpionate com-plexes Tp xCuL (Tpx = homoscorpionate ligand; L = acetonitrile or tetrahydrofuran, THF) and dimethyl sulfide (SMe2) in high yields and diasteroselectivities, and with activities higher (TOF = 46 h-1) than those already known with rhodium-or copper-based cata-lysts. Among the copper(I) homoscorpionate com-plexes tested, TpBr3Cu(NCCH 3) showed the highest catalytic activity under mild conditions. The catalytic activity is controlled by electronic effects induced by the Tp x ligand as well as by the stability of the TpxCu(SR 2) adducts. Indeed, in the case of TpMs as ligand, the TpMsCu(THT) (THT = tetrahydrothio-phene) and Tp MsCu(SMe2) species could be isolated as very stable crystalline solids, the molecular struc-ture of the former being confirmed by single-crystal X-ray diffraction analysis. The in situ generation of PhCHN 2 from benzaldehyde tosylhydrazone sodium salt at 60 °C in methyl tert-butyl ether as solvent and TpMsCu(THF) as the catalyst also showed high cata-lytic activities, improving those already reported with copper-based catalysts.

Structural and conformational analysis of 1-oxaspiro[2.5]octane and 1-oxa-2-azaspiro[2.5]octane derivatives by 1H, 13C, and 15N NMR

A structural and conformational analysis of 1-oxaspiro[2.5]octane and 1-oxa-2-azaspiro[2.5]octane derivatives was performed using 1H, 13C, and 15N NMR spectroscopy. The relative configuration and preferred conformations we

Novel biomimetic iron-catalysts for environmentally benign epoxidations of olefins

A new selective and easily manageable epoxidation method is presented using an inexpensive and efficient FeCl3·6H2O and imidazole derivatives as catalysts. Aqueous hydrogen peroxide as an environmentally benign oxidant is utilized. This novel Fe/imidazole system gives moderate to excellent yields toward aromatic mono-, di-, and tri-substituted olefins.

Process for the ruthenium-catalysed epoxidation of olefins by means of hydrogen peroxide

The present invention relates to a process for the epoxidation of olefins using catalysts based on ruthenium complexes in the presence of hydrogen peroxide.

Synthetic, spectral and catalytic activity studies of ruthenium bipyridine and terpyridine complexes: Implications in the mechanism of the ruthenium(pyridine-2,6-bisoxazoline)(pyridine-2,6-dicarboxylate)-catalyzed asymmetric epoxidation of olefins utilizing H2O2

Various Ru(L1)(L2) (1) complexes (L1 = 2,2′-bipyridines, 2,2′:6′,2″-terpyridines, 6-(4S)-4-phenyl-4,5-dihydro-oxazol-2-yl-2,2′-bipyridinyl or 2,2′-bipyridinyl-6-carboxylate; L2 = pyridine-2,6-dicarboxylate, pyridine-2-carboxylate or 2,2′-bipyridinyl-6-carboxylate) have been synthesized (or in situ generated) and tested on epoxidation of olefins utilizing 30% aqueous H2O2. The complexes containing pyridine-2,6-dicarboxylate show extraordinarily high catalytic activity. Based on the stereoselective performance of chiral ruthenium complexes containing non-racemic 2,2′-bipyridines including 6-[(4S)-4-phenyl-4,5-dihydro-oxazol-2-yl]-[2,2′]bipyridinyl new insights on the reaction intermediates and reaction pathway of the ruthenium-catalyzed enantioselective epoxidation are proposed. In addition, a simplified protocol for epoxidation of olefins using urea hydrogen peroxide complex as oxidizing agent has been developed.

PREPARATION OF ALPHA-HYDROXYKETONES

A process for the preparation of an 1, 1 -disubstituted oxirane is disclosed, wherein an organic sulphide is reacted in a polar solvent with an educt containing a leaving group attached to a primary or secondary carbon atom, and/or the sulfonium salt formed in this way is reacted with a ketone in presence of a base and a polar solvent. Oxiranes of the type obtained may be further converted into the corresponding α-hydroxyketone or α-aminoketone, either in one step by subjecting to aerobic oxidation in the presence of a transition metal catalyst, or in two steps by hydrolyzation in the presence of an aqueous acid to the corresponding dialcohol and subsequent selective oxidation. Further described are some novel epoxide intermediates. The α-hydroxyketones and α-aminoketones thus obtainable are useful inter alga as photoinitiators.

Convenient method for epoxidation of alkenes using aqueous hydrogen peroxide

(Chemical Equation Presented) The complex [Ru(tpy)(pydic)] (1a) is an active catalyst for epoxidation of alkenes by aqueous 30% hydrogen peroxide in tertiary alcohols. The protocol is simple to operate and gives the corresponding epoxides in good to excellent yields. Chiral enantiopure [Ru(tpy*)(pydic) ] complexes have been synthesized and successfully applied in this procedure.