27764-15-4

Upstream product

• 300-57-2 allylbenzene 
• 405-99-2 para-fluorostyrene 
• 588-56-7 (E)-1,2-di(4-fluorophenyl)ethene 
• 5216-31-9 1,2-bis(4-fluorophenyl)acetylene 
• 459-46-1 4-Fluorobenzyl bromide 
• 201230-82-2 carbon monoxide 
• 212058-54-3 (2R,3R)-2,3-Bis-(4-fluoro-phenyl)-oxirane 
• 459-57-4 4-fluorobenzaldehyde 
• 1643-73-8 (4-fluorobenzyl)magnesium chloride 
• 618-31-5 benzylidene dibromide 
• 349483-17-6 N-(4-fluorobenzylidene)-propan-1-amine 
• 352-11-4 1-chloromethyl-4-fluorobenzene 
• 3462-95-1 (4-fluorobenzyl)triphenylphosphonium chloride 
• 459-45-0 4-fluorobenzenediazonium tetrafluoroborate 

Downstream Products

• 458-76-4 4,4'-difluorobibenzyl 
• 327628-46-6 (2R,3S)-2,3-bis(4-fluorophenyl)oxirane 
• 51040-96-1 rac-cis-1,2-bis(4-fluorophenyl)cyclopropane 
• 1310814-30-2 1,3-bis(4-fluorophenyl)propane 
• 51009-43-9 rac-trans-1,2-bis(4-fluorophenyl)cyclopropane 
• 327628-49-9 (1S,2S)-2-chloro-1,2-bis(4-fluorophenyl)ethanol 
• 220091-30-5 (R,R)-(+)-1,2-di(p-fluorophenyl)ethane-1,2-diol 
• 588-56-7 (Z)-1,2-bis(4-fluorophenyl)ethylene 
• 1182735-03-0 [(4S,5S)-4,5-bis(4-fluorophenyl)-4,5-dihydroisoxazol-3-yl][(3aS,6R,7aR)-tetrahydro-8,8-dimethyl-2,2-dioxido-3H-3a,6-methano-2,1-benzisothiazol-1,(4H)-yl]methanone 
• 1448251-81-7 (E)-4,4'-(1-(2,5-dimethoxyphenyl)ethene-1,2-diyl)bis(fluorobenzene) 
• 1448251-82-8 (Z)-4,4'-(1-(2,5-dimethoxyphenyl)ethene-1,2-diyl)bis(fluorobenzene) 
• 1448251-83-9 (E)-4,4'-(1-(2,5-difluorophenyl)ethene-1,2-diyl)bis(fluorobenzene) 
• 1448251-84-0 (Z)-4,4'-(1-(2,5-difluorophenyl)ethene-1,2-diyl)bis(fluorobenzene) 
• 1448251-85-1 (E)-4,4'-(1-(2,4,6-trifluorophenyl)ethene-1,2-diyl)bis(fluorobenzene) 

Relevant academic research and scientific papers

Selenolate Anion as an Organocatalyst: Reactions and Mechanistic Studies

A new organocatalyst, the selenolate anion [RSe]–, generated from bench-stable and commercially available diphenyl diselenide or from phenyl benzyl selenide (10 mol%) is introduced. Benchmarking is performed in the conversion of benzylic chlorides into trans-stilbenes selectively at room temperature. Mechanistic studies support the intermediacy of the selenolate anion and of 1,2-diphenylethyl phenyl selenide. (Figure presented.).

AIR-STABLE NI(0)-OLEFIN COMPLEXES AND THEIR USE AS CATALYSTS OR PRECATALYSTS

The present invention relates to air stable, binary Ni(0)-olefin complexes and their use in organic synthesis.

Energy-Transfer-Mediated Photocatalysis by a Bioinspired Organic Perylenephotosensitizer HiBRCP

Energy transfer plays a special role in photocatalysis by utilizing the potential energy of the excited state through indirect excitation, in which a photosensitizer determines the thermodynamic feasibility of the reaction. Bioinspired by the energy-transfer ability of natural product cercosporin, here we developed a green and highly efficient organic photosensitizer HiBRCP (hexaisobutyryl reduced cercosporin) through structural modification of cercosporin. After structural manipulation, its triplet energy was greatly improved, and then, it could markedly promote the efficient geometrical isomerization of alkenes from the E-isomer to the Z-isomer. Moreover, it was also effective for energy-transfer-mediated organometallic catalysis, which allowed realization of the cross-coupling of aryl bromides and carboxylic acids through efficient energy transfer from HiBRCP to nickel complexes. Thus, the study on the relationship between structural manipulation and their photophysical properties provided guidance for further modification of cercosporin, which could be applied to more meaningful and challenging energy-transfer reactions.

Tuning the Selectivity of Palladium Catalysts for Hydroformylation and Semihydrogenation of Alkynes: Experimental and Mechanistic Studies

Here, we describe a selective palladium catalyst system for chemodivergent functionalization of alkynes with syngas. In the presence of an advanced ligand L2 bearing 2-pyridyl substituent as a built-in base, either hydroformylation or semihydrogenation of diverse alkynes occurs with high chemo- and stereoselectivity under comparable conditions. Mechanistic studies, including density functional theory (DFT) calculations, kinetic analysis, and control experiments, revealed that the strength and concentration of acidic cocatalysts play a decisive role in controlling the chemoselectivity. DFT studies disclosed that ligand L2 not only promotes heterolytic activation of hydrogen similar to frustrated Lewis pair (FLP) systems in the hydrogenolysis step for hydroformylation but also suppresses CO coordination to promote semihydrogenation under strong acid conditions. This switchable selectivity provides a strategy to design new catalysts for desired products.

Ni(4?Tbustb)3: A robust 16-electron Ni(0) olefin complex for catalysis

Sixteen-electron Ni(0) complexes bearing trans-stilbene derivative ligands have been shown to display a high degree of stability toward oxidation in the solid state. A structural analysis of a unique family of tris Ni(0) stilbene complexes revealed a remarkable effect of the steric hindrance of the substituents at the para position of the stilbene unit to temperature, oxidation, and degradation in solution. From these analyses, Ni(4?tBustb)3 arose as a long-term air-, bench-. and temperature-stable Ni(0) complex. Importantly, Ni(4?tBustb)3 presents faster kinetic profiles and a broader scope as a Ni(0) source, thus outperforming the previously described Ni(4?CF3stb)3 in a variety of relevant Ni-catalyzed transformations.

Photocatalyst-free visible light promoted: E → Z isomerization of alkenes

A simple and green method of visible light driven photocatalytic E to Z isomerization of alkenes has been developed. A variety of (Z)-alkenes can be prepared in the presence of visible light, without any additional photocatalyst. This protocol features photocatalyst-free conditions, which are mild, tolerant, and operationally simple, and is easy to implement.

Selenenate Anions (PhSeO?) as Organocatalyst: Synthesis of trans-Stilbenes and a PPV Derivative

The selenenate anion (RSeO?) is introduced as an active organocatalyst for the dehydrohalogen coupling of benzyl halides to form trans-stilbenes. It is shown that RSeO? is a more reactive catalyst than the previously reported sulfur analogues (sulfenate anion, RSO?) and selenolate anions (RSe?) in the aforementioned reaction. This catalytic system was also applied to the benzylic-chloromethyl-coupling polymerization (BCCP) of a bis-chloromethyl arene to form ppv (poly(p-phenylene vinylene))-type polymers with high yields, Mn (average molecular weight) up to 13,000 and ? (dispersity) of 1.15. (Figure presented.).

HIGHLY SELECTIVE ELECTROCHEMICAL HYDROGENATION OF ALKYNES

Disclosed are electrochemical methods to prepare an alkane or an alkene, such as a cis- alkene, from an alkyne, or an alkane from an alkene. The method utilizes an electrochemical cell having a cathode and an anode and a reactor.

Catalytic Transfer Hydrogenation Using Biomass as Hydrogen Source

We developed an operationally simple method for the direct use of biomass-derived chemical entities in a fundamentally important process, such as hydrogenation. Various carbohydrates, starch, and lignin were used for stereoselective hydrogenation. Employing a transition metal catalyst and a novel catalytic system, the reduction of alkynes, alkenes, and carbonyl groups with high yields was demonstrated. The regioselective hydrogenation to access different stereoisomers was established by simple variations in the reaction conditions. This work is based on an unprecedented catalytic system and represents a straightforward application of biomass as a reducing reagent in chemical reactions.

Copper-catalysed, diboron-mediated: Cis -dideuterated semihydrogenation of alkynes with heavy water

Methods to incorporate deuterium atoms into organic molecules are valuable for the pharmaceutical industry. Here, we found that diboron reagents can efficiently mediate the transfer of two D atoms from heavy water directly onto alkynes through copper-catalysed cis-selective semihydrogenation. Avoiding the use of costly and flammable D2 gas, this safe and practical process can proceed with excellent chemoselectivity and stereoselectivity. Utilizing the present method as the key step, the formal asymmetric total synthesis of d2-deuterium-labeled cis-combretastatin A4 is demonstrated. Mechanistic studies suggest that monoborylation of alkynes is the key step for this semihydrogenation process.