39153-68-9

Upstream product

• 1109274-16-9 o-(1-phenylethoxy)iodobenzene 
• 103-64-0 bromostyrene 
• 108-95-2 phenol 
• 100914-90-7 α-phenoxy-cinnamic acid 
• 100-52-7 benzaldehyde 
• 91388-23-7 Phenoxymethyl-triphenyl-phosphoniumchlorid 
• 67-56-1 methanol 
• 530-48-3 1,1-Diphenylethylene 
• 701-99-5 Phenoxyacetyl chloride 
• 766-94-9 vinyl phenyl ether 
• 100-34-5 benzene diazonium chloride 
• 588-72-7 [(E)-2-bromoethenyl]benzene 
• 4249-72-3 2-phenoxy-1-phenylethanol 
• 536-74-3 phenylacetylene 

Downstream Products

• 108-95-2 phenol 
• 100-41-4 ethylbenzene 
• 100-42-5 styrene 
• 17655-74-2 β-ethoxystyrene 
• 2074-04-6 phenylacetaldehyde-2,4-dinitrophenylhydrazone 
• 103-30-0 (E)-1,2-diphenyl-ethene 
• 645-49-8 cis-stilben 
• 4714-21-0 E-1-methyl-4-styryl-benzene 
• 1657-45-0 (Z)-4-methylstilbene 
• 14064-48-3 (E)-3-methylstilbene 
• 1694-19-5 E-1-(phenyl)-2-(4'-methoxyphenyl)ethene 
• 14064-41-6 (E)-3-methoxystilbene 
• 718-25-2 (E)-4-fluorostilbene 
• 2039-70-5 (E)-2-styrylnaphthalene 

Relevant academic research and scientific papers

Palladium-catalyzed synthesis of α-aryl acetophenones from styryl ethers and aryl diazonium saltsviaregioselective Heck arylation at room temperature

Preparation of α-aryl acetophenones from styryl ethers and aryldiazonium salts is described. The reaction is catalyzed by palladium acetate at room temperature in the absence of ligand and base. The developed method is highly attractive in terms of reaction conditions, substrate scope, functional group tolerance and yields. Synthetic applications of the present method are demonstrated by preparing α-aryl indoles and 3-aryl isocoumarin from styryl ethers.

Site-Selective Acceptorless Dehydrogenation of Aliphatics Enabled by Organophotoredox/Cobalt Dual Catalysis

The value of catalytic dehydrogenation of aliphatics (CDA) in organic synthesis has remained largely underexplored. Known homogeneous CDA systems often require the use of sacrificial hydrogen acceptors (or oxidants), precious metal catalysts, and harsh reaction conditions, thus limiting most existing methods to dehydrogenation of non- or low-functionalized alkanes. Here we describe a visible-light-driven, dual-catalyst system consisting of inexpensive organophotoredox and base-metal catalysts for room-temperature, acceptorless-CDA (Al-CDA). Initiated by photoexited 2-chloroanthraquinone, the process involves H atom transfer (HAT) of aliphatics to form alkyl radicals, which then react with cobaloxime to produce olefins and H2. This operationally simple method enables direct dehydrogenation of readily available chemical feedstocks to diversely functionalized olefins. For example, we demonstrate, for the first time, the oxidant-free desaturation of thioethers and amides to alkenyl sulfides and enamides, respectively. Moreover, the system's exceptional site selectivity and functional group tolerance are illustrated by late-stage dehydrogenation and synthesis of 14 biologically relevant molecules and pharmaceutical ingredients. Mechanistic studies have revealed a dual HAT process and provided insights into the origin of reactivity and site selectivity.

Cleavage of the lignin β-O-4 ether bond: Via a dehydroxylation-hydrogenation strategy over a NiMo sulfide catalyst

The efficient cleavage of lignin β-O-4 ether bonds to produce aromatics is a challenging and attractive topic. Recently a growing number of studies have revealed that the initial oxidation of CαHOH to CαO can decrease the β-O-4 bond dissociation energy (BDE) from 274.0 kJ mol-1 to 227.8 kJ mol-1, and thus the β-O-4 bond is more readily cleaved in the subsequent transfer hydrogenation, or acidolysis. Here we show that the first reaction step, except in the above-mentioned pre-oxidation methods, can be a Cα-OH bond dehydroxylation to form a radical intermediate on the acid-redox site of a NiMo sulfide catalyst. The formation of a Cα radical greatly decreases the Cβ-OPh BDE from 274.0 kJ mol-1 to 66.9 kJ mol-1 thereby facilitating its cleavage to styrene, phenols and ethers with H2 and an alcohol solvent. This is supported by control experiments using several reaction intermediates as reactants, analysis of product generation and by radical trap with TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) as well as by density functional theory (DFT) calculations. The dehydroxylation-hydrogenation reaction is conducted under non-oxidative conditions, which are beneficial for stabilizing phenol products.

Diarylrhodates as promising active catalysts for the arylation of vinyl ethers with grignard reagents

Anionic diarylrhodium complexes, generated by reacting [RhCl(cod)] 2 with 2 equiv of aryl Grignard reagents, were found to be effective active catalysts in cross-coupling reactions of vinyl ethers with aryl Grignard reagents, giving rise to the production of vinyl arenes. In this catalytic system, vinyl-O bonds were preferably cleaved over Ar-O or Ar-Br bonds. A lithium rhodate complex was isolated, and its crystal structure was determined by X-ray crystallography.

Pyrolysis of azetidinone derivatives: A versatile route towards electron-rich alkenes, C-1 allylation and/or homologation of aldehydes

Pyrolysis of β-lactams and β-thiolactams led essentially to stereoselective synthesis of the high energy electron-rich Z-alkenes. Extension of this methodology to the pyrolysis of 3-allyloxy derivatives gave a simple direct route to the synthetically important 4-pentenal. These pyrolytic transformations convert aldehydes to aryloxyalkenes (a protected homologation) and 4-pentenal (a C-1 allylation and homologation). The starting 3-aryloxy and 3-allyloxy-β-lactams were synthesized by the standard Staudinger ketene-imine [2 + 2] cycloaddition. The corresponding β-thiolactams have readily been obtained in good yields by thiation of β-lactams with Lawesson's reagent. This journal is the Partner Organisations 2014.

Regioselective and stereoselective entry to β,β-disubstituted vinyl ethers via the sequential hydroboration/Suzuki-Miyaura coupling of ynol ethers

A highly regio- and stereoselective synthesis of stereodefined β,β-disubstituted alkenyl ethers featuring the sequential hydroboration/Suzuki-Miyaura coupling of ynol ethers has been described. A number of functional groups, including OMe, Ac, CO2Et, CN, halides, and alkyl, (hetero)aryl, and alkenyl groups, are well-tolerated under the reaction conditions. Furthermore, it allows a facile entry to the labile diarylacetaldehydes by TFA-mediated hydrolysis of β,β-disubstituted vinyl ethers.

Chemo-selective copper-catalyzed C-O coupling reactions of phenols with aryl/vinyl halides using enaminone as efficient ligand

The copper-catalyzed Ullmann C-O coupling reactions between phenols and aryl/vinyl halides have been efficiently performed by employing (E)-3-(dimethylamino)-1-(2-hydroxyphenyl)prop-2-en-1-one, an easily available enaminone, as ligand. This new ligand is advantageous for its easy availability, broad applicability and good efficiency. Copyright 2012 John Wiley & Sons, Ltd. Copyright

Three component reaction of arynes with cyclic ethers and active methines: Synthesis of ω-trichloroalkyl phenyl ethers

Synthesis of ω-chlorinated alkyl phenyl ethers by tandem reaction of arynes with cyclic ethers and active methines was achieved. Reaction of benzenediazonium 2-carboxylate with tetrahydropyran or tetrahydrofuran in refluxing chloroform afforded 6,6,6-trichlorohexyl phenyl ether or 5,5,5-trichloropentyl phenyl ether in 40% and 61% yields, respectively. When dichloroacetonitrile was used as a reactant, 5,5-dichloro-5-cyanopentyl phenyl ether was obtained in 61% yield. While benzenediazonium carboxylate did not react with epoxides, reaction of benzyne derived from 2-(trimethylsilyl)phenyl triflate with epoxides afforded 3,3,3-trichloropropyl phenyl ethers in good yields as isomeric mixtures. The reaction of oxetanes with benzyne was also reported.

Catalytic dehydrogenation of o-alkylated or o-alkoxylated iodoarenes with concomitant hydrogenolysis

Palladium-catalyzed dehydrogenation of suitable chains bonded to an ortho position of an iodoarene has been achieved by two methods both involving oxidative addition of the iodoarene to palladium(0) and palladacycle formation under mild conditions.

Reaction of benzyne with styrene oxide: Insertion of arynes into a C-O bond of epoxides

Benzyne inserts into one of the C-O bonds of styrene oxide to form a dihydrobenzofuran as the major product together with five other reaction products. A detailed study of the reaction mixture clarified an intriguing forty-year-old personal communication from Stiles and Haag. Georg Thieme Verlag Stuttgart.