42006-43-9

Upstream product

• 455-13-0 4-Iodobenzotrifluoride 
• 1813-97-4 1-allyl-4-(trifluoromethyl)benzene 
• 455-19-6 4-Trifluoromethylbenzaldehyde 
• 1530-32-1 ethyltriphenylphosphonium bromide 
• 1754-88-7 ethylenetriphenylphosphorane 
• 91118-30-8 1-(prop-1-en-1-yl)-4-(trifluoromethyl)benzene 
• 402-50-6 1-trifluoromethyl-4-vinyl-benzene 
• 1042728-31-3 1-(bis(trimethylsilyl)methyl)-1-methyl-3-phenylurea 

Downstream Products

• 91118-30-8 cis-l-(p-trifluoromethyl-phenyl)-propen 
• 24654-53-3 (E)-3-(4-(trifluoromethyl)phenyl)-2-propenenitrile 
• 1130490-94-6 4,4,5,5-tetramethyl-2-(1-(4-trifluoromethylphenyl)propan-2-yl)-1,3,2-dioxaborolane 
• 711-33-1 4-trifluoromethyl propiophenone 
• 713-45-1 1-[(4-trifluoromethyl)phenyl]-2-propanone 

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.

Catalytic, Enantioselective Syn-Oxyamination of Alkenes

The chemo-, regio-, diastereo-, and enantioselective 1,2-oxyamination of alkenes using selenium(II/IV) catalysis with a chiral diselenide catalyst is reported. This method uses N-tosylamides to generate oxazoline products that are useful both as protected

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.

A Next-Generation Air-Stable Palladium(I) Dimer Enables Olefin Migration and Selective C?C Coupling in Air

We report a new air-stable PdI dimer, [Pd(μ-I)(PCy2tBu)]2, which triggers E-selective olefin migration to enamides and styrene derivatives in the presence of multiple functional groups and with complete tolerance of air. The same dimer also triggers extremely rapid C?C coupling (alkylation and arylation) at room temperature in a modular and triply selective fashion of aromatic C?Br, C?OTf/OFs, and C?Cl bonds in poly(pseudo)halogenated arenes, displaying superior activity over previous PdI dimer generations for substrates that bear substituents ortho to C?OTf.

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.

Controllable Isomerization of Alkenes by Dual Visible-Light-Cobalt Catalysis

We report herein that thermodynamic and kinetic isomerization of alkenes can be accomplished by the combination of visible light with Co catalysis. Utilizing Xantphos as the ligand, the most stable isomers are obtained, while isomerizing terminal alkenes over one position can be selectively controlled by using DPEphos as the ligand. The presence of the donor–acceptor dye 4CzIPN accelerates the reaction further. Transformation of exocyclic alkenes into the corresponding endocyclic products could be efficiently realized by using 4CzIPN and Co(acac)2 in the absence of any additional ligands. Spectroscopic and spectroelectrochemical investigations indicate CoI being involved in the generation of a Co hydride, which subsequently adds to alkenes initiating the isomerization.

E-Olefins through intramolecular radical relocation

Full control over the selectivity of carbon-carbon double-bond migrations would enable access to stereochemically defined olefins that are central to the pharmaceutical, food, fragrance, materials, and petrochemical arenas. The vast majority of double-bond migrations investigated over the past 60 years capitalize on precious-metal hydrides that are frequently associated with reversible equilibria, hydrogen scrambling, incomplete E/Z stereoselection, and/or high cost. Here, we report a fundamentally different, radical-based approach.We showcase a nonprecious, reductant-free, and atom-economical nickel (Ni)(I)-catalyzed intramolecular 1,3-hydrogen atom relocation to yield E-olefins within 3 hours at room temperature. Remote installations of E-olefins over extended distances are also demonstrated.

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.

A Stereoconvergent Cyclopropanation Reaction of Styrenes

The first stereoconvergent cyclopropanation reaction by means of photoredox catalysis using diiodomethane as the methylene source is described. This transformation exhibits broad functional group tolerance and it is characterized by an excellent stereocontrol en route to trans-cyclopropanes regardless of whether E- or Z-styrene substrates were utilized.

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.