2077-34-1

Upstream product

• 2077-33-0 1-methyl-2-[(1Z)-prop-1-en-1-yl]benzene 
• 1530-32-1 ethyltriphenylphosphonium bromide 
• 529-20-4 2-methylphenyl aldehyde 
• 1587-04-8 1-methyl-2-(2-propenyl)-benzene 
• 27546-46-9 2-methyl-1-cyclopropylbenzene 
• 345942-00-9 bis-<2-(n-propylthio)benzyl> oxalate 
• 4736-60-1 ethyltriphenylphosphonium iodide 
• 1530-36-5 [(2-methylphenyl)methyl]triphenylphosphonium bromide 
• 75-07-0 acetaldehyde 
• 134749-76-1 Triphenyl-(1-o-tolylmethanesulfonyl-ethylidene)-λ⁵-phosphane 
• 95-46-5 2-methylphenyl bromide 
• 24850-33-7 allyltributylstanane 
• 513-35-9 2-methyl-but-2-ene 

Downstream Products

• 2077-33-0 1-methyl-2-[(1Z)-prop-1-en-1-yl]benzene 
• 134522-51-3 (1R,5R,6R,7R)-3-Hydroxy-6-methyl-7-o-tolyl-bicyclo[3.2.1]oct-3-ene-2,8-dione 
• 26155-19-1 (2E)-3-(2-methylphenyl)-2-propenenitrile 
• 1130490-95-7 4,4,5,5-tetramethyl-2-(1-o-tolylpropan-2-yl)-1,3,2-dioxaborolane 

Relevant academic research and scientific papers

Iron Catalyzed Double Bond Isomerization: Evidence for an FeI/FeIII Catalytic Cycle

Iron-catalyzed isomerization of alkenes is reported using an iron(II) β-diketiminate pre-catalyst. The reaction proceeds with a catalytic amount of a hydride source, such as pinacol borane (HBpin) or ammonia borane (H3N?BH3). Reactivity with both allyl arenes and aliphatic alkenes has been studied. The catalytic mechanism was investigated by a variety of means, including deuteration studies, Density Functional Theory (DFT) and Electron Paramagnetic Resonance (EPR) spectroscopy. The data obtained support a pre-catalyst activation step that gives access to an η2-coordinated alkene FeI complex, followed by oxidative addition of the alkene to give an FeIII intermediate, which then undergoes reductive elimination to allow release of the isomerization product.

Tandem Olefin Isomerization/Cyclization Catalyzed by Complex Nickel Hydride and Br?nsted Acid

We disclose a nickel/Br?nsted acid-catalyzed tandem process consisting of double bond isomerization of allyl ethers and amines and subsequent intramolecular reaction with nucleophiles. The process is accomplished by [(Me3P)4NiH]N(SO2CF3)2 in the presence of triflic acid. The methodology provides rapid access to tetrahydropyran-fused indoles and other oxacyclic scaffolds under very low catalyst loadings.

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.

Radical Cation Diels-Alder Reactions by TiO2 Photocatalysis

Radical cation Diels-Alder reactions by titanium dioxide (TiO2) photocatalysis in lithium perchlorate/nitromethane solution are described. TiO2 photocatalysis promotes reactions between electron-rich dienes and dienophiles, which would otherwise be difficult to accomplish due to electronic mismatching. The reactions are triggered by hole oxidation of the dienophile and are completed by the excited electron reduction of the radical cation intermediate at the dispersed surface in the absence of any sacrificial substrate.

PICOLINAMIDES AS FUNGICIDES

This disclosure relates to picolinamides of Formula I and their use as fungicides.

Nitrogen-Doped Carbon-Encapsulated Nickel/Cobalt Nanoparticle Catalysts for Olefin Migration in Allylarenes

Olefin migration in allylarenes is typically performed with precious-metal-based homogeneous catalysts. In contrast, very limited progress has been made with the use of cheap, Earth-abundant base metals as heterogeneous catalysts for these transformations—in spite of the obvious economic and environmental advantages. Herein, we report on the use of an easily prepared heterogeneous catalyst material for the migration of olefins, in particular, for allylarenes. The catalyst material consists of nickel/cobalt alloy nanoparticles encapsulated in nitrogen-doped carbon shells. The encapsulated nanoparticles are stable in air and are easily collected by centrifugation, filtration, or magnetic separation. Furthermore, we demonstrate that the catalysts can be reused several times and provide continuously high yields of the olefin-migration product.

Nickel-Catalyzed Allylic C(sp2)–H Activation: Stereoselective Allyl Isomerization and Regiospecific Allyl Arylation of Allylarenes

Stereoselective allyl isomerization and regiospecific allyl arylation reactions of allylarenes with a catalytic system comprising nickel(II) with an aryl Grignard reagent were studied. Both reactions are triggered by allylic internal C(sp2)–H activation by in-situ-formed Ni0, which is inserted into the C–H bond at the 2-position of the allyl moiety without a directing group. The isomerization of allylarene to 1-propenylarene favors the E isomer and proceeds with quantitative conversion. The arylation takes place through oxidative cross-coupling of allylarenes with excess Grignard reagent. It occurs regiospecifically at the position of C(sp2)–H activation and represents a new method for the synthesis of 1,1-disubstituted olefins. The results of deuterium labeling experiments reveal an alkenyl/alkyl mechanism involving allylic internal C(sp2)–H activation and multiple intermolecular 1,2-, 1,3-, and 2,3-hydride shifts. These methods represent new approaches to the functionalization of olefins, and the mechanistic investigations could be helpful for the discovery and design of new strategies for olefin functionalization.

Direct organocatalytic oxo-metathesis, a trans-selective carbocation-catalyzed olefination of aldehydes

A direct organocatalytic carbonyl/olefin oxo-metathesis has been developed. The reaction is catalyzed by trityl tetrafluoroborate (TrBF4) and utilizes unactivated alkenes for the olefination of aromatic aldehydes to give trans β-alkylstyrenes in yields of 44-85% with only acetone as the byproduct. The pronounced Lewis acidity of the carbocation results in unusual reactivity that is proposed to catalyze a stepwise [2+2] cycloaddition to give an oxetane intermediate. Fragmentation of the latter in a formal retro [2+2] reaction gives the oxo-metathesis product.

A facile and convenient sequential homobimetallic catalytic approach towards β-methylstyrenes. A one-pot Stille cross-coupling/isomerization strategy

An efficient one-pot synthetic approach towards β-methylstyrenes is reported. The transformation, based on sequential homobimetallic catalysis, involves a Stille cross-coupling reaction between aryl halides and allyltributylstannane, followed by an in situ palladium-catalyzed conjugative isomerization. The reaction was optimized, and the best results were obtained with 10 mol% Pd(PPh3)2Cl2, 8.0 equiv. LiCl, and 0.5 equiv. PPh3 in diglyme at 130 °C for 12 h. It was demonstrated that the reaction tolerates a wide variety of functional groups. This journal is the Partner Organisations 2014.

Wittig reaction: Role of steric effects in explaining the prevalent formation of Z olefin from nonstabilized ylides

For understanding the mechanism involved in the Wittig reaction, it is important to know the factors which influence the stability of 1,2-oxaphosphetane intermediates with pentacoordinate phosphorus; in these intermediates, the steric factor plays a predominant role. Studying the Wittig reaction between nonstabilized ylides and different aldehydes, we noted that the stereochemical outcome driving toward Z-olefin formation was influenced only by different steric factors. The proposed mechanism differs from those previously reported because it underlines the fundamental role of the two cis/trans oxaphosphetane intermediates with the oxygen atom in equatorial position.