197957-64-5

Upstream product

• 100-52-7 benzaldehyde 
• 100-42-5 styrene 
• 104-95-0 (4-bromophenyl)thioanisole 
• 104-96-1 4-methylsulfanylaniline 
• 39153-68-9 (E,Z)-β-phenoxystyrene 
• 18620-04-7 4-thioanisolemagnesium bromide 
• 140-29-4 phenylacetonitrile 
• 3446-90-0 4-(methylthio)benzyl alcohol 
• 35371-03-0 4-iodothioanisole 
• 536-74-3 phenylacetylene 
• 33533-42-5 1-[4-(methylsulfanyl)phenyl]-2-phenylacetylene 
• 3446-89-7 4-(Methylthio)benzaldehyde 
• 16721-45-2 triphenyl(phenylmethylene)phosphorane 
• 64-19-7 acetic acid 

Downstream Products

• 186819-08-9 4,4-Dimethyl-3-(4-methylsulfonylphenyl)-2-phenyl-2-cyclobuten-1-ol 
• 186819-03-4 4,4-Dimethyl-3-(4-methylsulfonylphenyl)-2-phenyl-2-cyclobuten-1-one 

Relevant academic research and scientific papers

Dinuclear cobalt complex-catalyzed stereodivergent semireduction of alkynes: Switchable selectivities controlled by H2O

Catalytic semireduction of internal alkynes to alkenes is very important for organic synthesis. Although great success has been achieved in this area, switchable Z/E stereoselectivity based on a single catalyst for the semireduction of internal alkynes is a longstanding challenge due to the multichemo- and stereoselectivity, especially based on less-expensive earth-abundant metals. Herein, we describe a switchable semireduction of alkynes to (Z)- or (E)-alkenes catalyzed by a dinuclear cobalt complex supported by a macrocyclic bis pyridyl diimine (PDI) ligand. It was found that cis-reduction of the alkyne occurs first and the Z-E alkene stereoisomerization process is formally controlled by the amount of H2O, since the concentration of H2O may influence the catalytic activity of the catalyst for isomerization. Therefore, this protocol provides a facile way to switch to either the (Z)- or (E)-olefin isomer in a single transformation by adjusting the amount of water.

Tandem Acceptorless Dehydrogenative Coupling-Decyanation under Nickel Catalysis

The development of new catalytic processes based on abundantly available starting materials by cheap metals is always a fascinating task and marks an important transition in the chemical industry. Herein, a nickel-catalyzed acceptorless dehydrogenative coupling of alcohols with nitriles followed by decyanation of nitriles to access diversely substituted olefins is reported. This unprecedented C=C bond-forming methodology takes place in a tandem manner with the formation of formamide as a sole byproduct. The significant advantages of this strategy are the low-cost nickel catalyst, good functional group compatibility (ether, thioether, halo, cyano, ester, amino, N/O/S heterocycles; 43 examples), synthetic convenience, and high reaction selectivity and efficiency.

Proton-Coupled Electron Transfer: Transition-Metal-Free Selective Reduction of Chalcones and Alkynes Using Xanthate/Formic Acid

Highly chemoselective reduction of α,β-unsaturated ketones to saturated ketones and stereoselective reduction of alkynes to (E)-alkenes has been developed under a transition-metal-free condition using a xanthate/formic acid mixture through proton-coupled electron transfer (PCET). Mechanistic experiments and DFT calculations support the possibility of a concerted proton electron-transfer (CPET) pathway. This Birch-type reduction demonstrates that a small nucleophilic organic molecule can be used as a single electron-transfer (SET) reducing agent with a proper proton source.

Transition-Metal-Free Highly Chemoselective and Stereoselective Reduction with Se/DMF/H2O System

A novel metal-free reduction system, in which H2Se (or HSe-) produced in situ from Se/DMF/H2O acts as the active reducing species, has been developed. By using water as an inexpensive, safe, and environmentally friendly surrogate as the hydrogen donor, this new reduction system incorporating Se/DMF/H2O displayed high selectivity and good activity in the reduction of α,β-unsaturated ketones and alkynes. Therefore, this reduction system has great potential to be a general and practical reduction methodology in organic transformation.

Palladium-Catalyzed Reductive Coupling Reaction of Terminal Alkynes with Aryl Iodides Utilizing Hafnocene Difluoride as a Hafnium Hydride Precursor Leading to trans-Alkenes

Herein, we describe a reductive cross-coupling of alkynes and aryl iodides by using a novel catalytic system composed of a catalytic amount of palladium dichloride and a promoter precursor, hafnocene difluoride (Cp2HfF2, Cp=cyclopentadienyl anion), in the presence of a mild reducing reagent, a hydrosilane, leading to a one-pot preparation of trans-alkenes. In this process, a series of coupling reactions efficiently proceeds through the following three steps: (i) an initial formation of hafnocene hydride from hafnocene difluoride and the hydrosilane, (ii) a subsequent hydrohafnation toward alkynes, and (iii) a final transmetalation of the alkenyl hafnium species to a palladium complex. This reductive coupling could be chemoselectively applied to the preparation of trans-alkenes with various functional groups, such as an alkyl group, a halogen, an ester, a nitro group, a heterocycle, a boronic ester, and an internal alkyne.

Nickel-catalyzed synthesis of (E)-olefins from benzylic alcohol derivatives and arylacetonitriles via C-O activation

An efficient Ni-catalyzed synthesis of (E)-olefins using the readily available benzylic alcohol derivatives and arylacetonitriles is described. This transformation should proceed via a tandem process involving nickel-catalyzed cross coupling via C-O activation and subsequent stereoselective E2 elimination.

N,N′-Mono substituted acyclic thioureas: Efficient ligands for the palladium catalyzed Heck reaction of deactivated aryl bromides

A series of N,N′-mono substituted acyclic thiourea ligands are found to be highly active phosphine-free catalysts for palladium catalyzed Heck reaction of aryl iodides and bromides with olefins. We have achieved high turnover numbers for aryl iodides with olefins (TONs up to 970,000 for the reaction of iodobenzene with styrene).

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.

Mizoroki-Heck reactions catalyzed by palladium dichloro-bis(aminophosphine) complexes under mild reaction conditions. the importance of ligand composition on the catalytic activity

Dichloro-bis(aminophosphine) complexes of palladium with the general formula [(P{(NC5H10)3-n(C6H 11)n})2Pd(Cl)2] (where n = 0-2) are easily accessible, cheap and air stable, highly active and universally applicable C-C cross-coupling catalysts, which exhibit an excellent functional group tolerance. The ligand composition of amine-substituted phosphines (controlled by the number of P-N bonds) was found to effectively determine their catalytic activity in the Heck reaction, for which nanoparticles were demonstrated to be their catalytically active form. While dichloro{bis[1, 1′,1′′-(phosphinetriyl)tripiperidine]}palladium (1), the least stable complex (towards protons) within the series of [(P{(NC5H 10)3-n(C6H11)n}) 2Pd(Cl)2] (where n = 0-3), is a highly active Heck catalyst at 100 °C and, hence, a rare example of an effective and versatile Heck catalyst that efficiently operates under mild reaction conditions (100 °C or below), a significant successive drop in activity was noticed for dichloro-bis(1,1′-(cyclohexylphosphinediyl)dipiperidine)palladium (2, with n = 1), dichloro-bis(1-(dicyclohexylphosphinyl)piperidine)palladium (3, with n = 2) and dichloro-bis(tricyclohexylphosphine)palladium (4, with n = 3), of which the latter is essentially inactive (at least under the reaction conditions applied). This trend was explained by the successively increasing complex stability and its ensuing retarding effect on the (water-induced) generation of palladium nanoparticles thereof. This interpretation was experimentally confirmed (initial reductions of 1-4 into palladium(0) complexes of the type [Pd(P{(NC5H10)3-n(C6H 11)n})2] (where n = 0-3) were excluded to be the reason for the activity difference observed as well as molecular (Pd 0/PdII) mechanisms were excluded to be operative) and thus demonstrates that the catalytic activity of dichloro-bis(aminophosphine) complexes of palladium can-in reactions where nanoparticles are involved-effectively be controlled by the number of P-N bonds in the ligand system.

Novel 1,2-diarylcyclobutenes: Selective and orally active COX-2 inhibitors

A series of novel 2,3-diaryl-2-cyclobuten-1-ones have been synthesized and have been evaluated with respect to their ability to inhibit the isozymes of cyclooxygenase, COX-1 and COX-2. 4,4-Dimethyl-2-phenyl-3-[4-(methylsulfonyl)phenyl]cyclobutenone 22 was found to be highly selective for inhibition of COX-2 and was orally active (ED50 = 2.4 mg/kg) in the rat paw edema model.