1879-53-4

Upstream product

• 6285-05-8 4'-chloropropiophenone 
• 1745-18-2 1-allyl-4-chlorobenzene 
• 17847-85-7 triethyl(ethylidene)phosphorane 
• 104-88-1 4-chlorobenzaldehyde 
• 1017-88-5 dimethyldiphenylphosphonium iodide 
• 100-52-7 benzaldehyde 
• 1754-88-7 ethylenetriphenylphosphorane 
• 587-04-2 m-Chlorobenzaldehyde 
• 1073-67-2 4-vinylbenzyl chloride 
• 917-54-4 methyllithium 
• 4736-60-1 ethyltriphenylphosphonium iodide 
• 74-88-4 methyl iodide 
• 1202-60-4 -2-methyl-3-(4-chlorophenyl)prop-2-enoic acid 
• 1135821-12-3 ethyl-(2-methoxy-phenyl)-diphenyl-phosphonium; iodide 

Relevant academic research and scientific papers

Method for synthesizing 1, 2-disubstituted olefin through reaction of terminal group olefin and sulfoxide

The invention discloses a method for synthesizing 1, 2-disubstituted olefin by reaction of terminal olefin and sulfoxide. According to the method, terminal olefin with sulfoxide make reaction in one pot in the presence of ferric salt and hydrogen peroxide to generate the 1, 2-disubstituted olefin. sulfoxide is simultaneously used as a hydrocarbylation reagent and a solvent of olefin, and a reaction product is 1, 2-disubstituted olefin of which a terminal carbon atom in terminal olefin is coupled with a sulfoxide alkyl group, so that an olefin carbon chain is increased; the reaction conditionsare mild, the selectivity is high, the yield is high, and industrial production is facilitated.

Facile Synthesis of Chiral Arylamines, Alkylamines and Amides by Enantioselective NiH-Catalyzed Hydroamination

Regio- and enantioselective hydroarylamination, hydroalkylamination and hydroamidation of styrenes have been developed by NiH catalysis with a simple bioxazoline ligand under mild conditions. A wide range of enantioenriched benzylic arylamines, alkylamines and amides can be easily accessed by nitroarenes, hydroxylamines and dioxazolones, respectively as amination reagents. The chiral induction in these reactions is proposed to proceed through an enantiodifferentiating syn-hydronickellation step.

A donor-acceptor complex enables the synthesis of: E -olefins from alcohols, amines and carboxylic acids

Olefins are prevalent substrates and functionalities. The synthesis of olefins from readily available starting materials such as alcohols, amines and carboxylic acids is of great significance to address the sustainability concerns in organic synthesis. Metallaphotoredox-catalyzed defunctionalizations were reported to achieve such transformations under mild conditions. However, all these valuable strategies require a transition metal catalyst, a ligand or an expensive photocatalyst, with the challenges of controlling the region- and stereoselectivities remaining. Herein, we present a fundamentally distinct strategy enabled by electron donor-acceptor (EDA) complexes, for the selective synthesis of olefins from these simple and easily available starting materials. The conversions took place via photoactivation of the EDA complexes of the activated substrates with alkali salts, followed by hydrogen atom elimination from in situ generated alkyl radicals. This method is operationally simple and straightforward and free of photocatalysts and transition-metals, and shows high regio- and stereoselectivities.

Electro-mediated PhotoRedox Catalysis for Selective C(sp3)–O Cleavages of Phosphinated Alcohols to Carbanions

We report a novel example of electro-mediated photoredox catalysis (e-PRC) in the reductive cleavage of C(sp3)?O bonds of phosphinated alcohols to alkyl carbanions. As well as deoxygenations, olefinations are reported which are E-selective and can be made Z-selective in a tandem reduction/photosensitization process where both steps are photoelectrochemically promoted. Spectroscopy, computation, and catalyst structural variations reveal that our new naphthalene monoimide-type catalyst allows for an intimate dispersive precomplexation of its radical anion form with the phosphinate substrate, facilitating a reactivity-determining C(sp3)?O cleavage. Surprisingly and in contrast to previously reported photoexcited radical anion chemistries, our conditions tolerate aryl chlorides/bromides and do not give rise to Birch-type reductions.

Process for isomerizing and converting (Z)-olefins to (E)-olefins

The invention belongs to the technical field of metal catalytic synthesis, and discloses a method for isomerizing and converting (Z)-olefins into (E)-olefins. The (E)-olefins are prepared through a reaction at -30-80 DEG C for 0.5-48 h by using a combination of CoX2 and a PNP or PAO ligand as a catalyst in the presence of an activating reagent; and a molar ratio of the (Z)-olefins to the CoX2 to the PNP or PAO ligand to the activating reagent is 1:(0.00001-0.10):(0.00001-0.10):(0.00003-0.30). The catalyst used in the invention is the combination of the cheap metal cobalt salt and the simple and easily available ligand, no other toxic transition metal (such as ruthenium, rhodium and palladium) salt is added in the reaction, and the method also has the advantages of cheap and easily available raw material, good functional group tolerance, mild reaction conditions, simplicity in operation, and e atom economy of 100%.

Superelectrophilic Fe(III)-Ion Pairs as Stronger Lewis Acid Catalysts for (E)-Selective Intermolecular Carbonyl-Olefin Metathesis

An intermolecular carbonyl-olefin metathesis reaction is described that relies on superelectrophilic Fe(III)-based ion pairs as stronger Lewis acid catalysts. This new catalytic system enables selective access to (E)-olefins as carbonyl-olefin metathesis products. Mechanistic investigations suggest the regioselective formation and stereospecific fragmentation of intermediate oxetanes to be the origin of this selectivity. The optimized conditions are general for a variety of aryl aldehydes and trisubstituted olefins and are demonstrated for 28 examples in up to 64% overall yield.

Cobalt-Catalyzed Z to e Isomerization of Alkenes: An Approach to (E)-β-Substituted Styrenes

An efficient cobalt-catalyzed Z to E isomerization of β-substituted styrenes using the amido-diphosphine ligand was developed, delivering the (E)-isomers with good functional tolerance and high stereoselectivity. The reaction could be scaled up to gram-scale with a catalyst loading of 0.1 mol %, using a mixture of (Z)- and (E)-alkene as the starting material. Preliminary mechanistic studies indicated that cobalt(I)-hydride and a benzylic-cobalt species were probably involved in the reaction, as supported by experiments and DFT calculations.

Palladium-Catalyzed Methylation of Aryl, Heteroaryl, and Vinyl Boronate Esters

A method for the direct methylation of aryl, heteroaryl, and vinyl boronate esters is reported, involving the reaction of iodomethane with aryl-, heteroaryl-, and vinylboronate esters catalyzed by palladium and PtBu2Me. This transformation occurs with a remarkably broad scope and is suitable for late-stage derivatization of biologically active compounds via the boronate esters. The unique capabilities of this method are demonstrated by combining carbon-boron bond-forming reactions with palladium-catalyzed methylation in a tandem transformation.

OXADIAZINE COMPOUNDS AND METHODS OF USE THEREOF

The present disclosure relates to oxadiazine compounds, pharmaceutical compositions comprising an effective amount of an oxadiazine compound and methods for using an oxadiazine compound in the treatment of a neurodegenerative disease, comprising administering to a subject in need thereof an effective amount of an oxadiazine compound.

(E)-Selective Wittig Reactions between a Nonstabilized Phosphonium Ylide Bearing a Phosphastibatriptycene Skeleton and Benzaldehydes

Wittig reactions between benzaldehyde derivatives and a nonstabilized phosphonium ylide bearing a phosphastibatriptycene skeleton, regarded as a tridentate aryl ligand, gave (E)-alkenes with high selectivity in the presence of both lithium and sodium salts. As previously reported, reactions between a triphenylphosphonium ylide and benzaldehyde derivatives under the same conditions afforded mainly (Z)-alkenes. Variable-temperature (VT)31P{1H} NMR spectra showed two signals, assigned to cis- and trans-1,2-oxaphosphetanes, which were observed at different temperatures (–80 °C and –40 °C, respectively) in the Wittig reaction between benzaldehyde and the nonstabilized phosphonium ylide bearing the phosphastibatriptycene skeleton, in the presence of both lithium and sodium salts, and showed the existence of equilibrium between these products at –40 °C. On the other hand, this equilibrium was not clearly observed in the reaction between the triphenylphosphonium ylide and benzaldehyde, for which only one signal was detected. The observed intermediates were confirmed to be 1,2-oxaphosphetanes by deprotonation of the isolated β-hydroxyalkylphosphonium salts bearing a phosphastibatriptycene skeleton and a triphenylphosphine moiety, respectively. Crossover reactions were conducted in the deprotonations of β-hydroxyalkylphosphonium salts with TMS2NNa in the presence of p-chlorobenzaldehyde, resulting in the observation of signals corresponding to 1,2-oxaphosphetanes containing phenyl and p-chlorophenyl groups at the 4-positions, indicating the exchange process between benzaldehyde and p-chlorobenzaldehyde at –40 °C for the phosphastibatriptycene system and at 0 °C for triphenyl derivatives. These results clearly indicated that stereochemical drift occurred at those temperatures, even in reactions using nonstabilized phosphonium ylides. The stereochemical drift in the phosphastibatriptycene system occurred at a lower temperature than in the case of the triphenyl derivative, thus explaining the (E)-selective Wittig reactions between the benzaldehyde derivatives and the nonstabilized phosphastibatriptycene-based phosphonium ylide in the presence of lithium and sodium salts.