6185-76-8

Upstream product

• 87901-71-1 α-(4-methoxyphenyl)(4-trifluoromethyl)benzyl alcohol 
• 696-62-8 para-iodoanisole 
• 104-92-7 1-bromo-4-methoxy-benzene 
• 455-18-5 4-CF₃C₆H₄CN 
• 181308-89-4 1-(4-methoxyphenyl)-2-[4-(trifluoromethyl)phenyl]ethanone 
• 100-07-2 4-methoxy-benzoyl chloride 
• 3471-32-7 4-Methoxyphenylhydrazine 
• 455-24-3 4-trifluoromethylbenzoic acid 
• 13139-86-1 4-methoxyphenyl magnesium bromide 
• 116332-61-7 N-methoxy-N-methyl-4-trifluoromethylbenzamide 
• 402-43-7 p-trifluoromethylphenyl bromide 
• 329-15-7 4-trifluoromethyl-phenyl acetyl chloride 
• 100-66-3 methoxybenzene 
• 6343-26-6 1-(4-Methoxybenzoyl)pyrrolidine-2,5-dione 

Downstream Products

• 429677-24-7 (4-trifluoromethyl-4'-methoxydiphenyl)methanol-α-D 
• 915750-78-6 3-(p-methoxyphenyl)-3-[(p-trifluoromethyl)phenyl]-3-hydroxy-2-methylpropionate 
• 915750-79-7 methyl 3-[(p-trifluoromethyl)phenyl]-2-methyl-p-methoxycinnamate 
• 915750-81-1 (Z)-1,1-dideuterio-3-(p-methoxyphenyl)-3-[(p-trifluoromethyl)phenyl]-2-methylprop-2-en-1-ol 
• 1638192-44-5 1-(2,2-difluoro-1-(4-(trifluoromethyl)phenyl)vinyl)-4-methoxybenzene 
• 87901-71-1 α-(4-methoxyphenyl)(4-trifluoromethyl)benzyl alcohol 
• 41831-09-8 [1-(4-Methoxy-phenyl)-1-(4-trifluoromethyl-phenyl)-meth-(Z)-ylidene]-hydrazine 
• 1312211-12-3 C₁₈H₁₇F₃O₂ 

Relevant academic research and scientific papers

The effect of a para substituent on the conformational preference of 2,2-diphenyl-1,3-dioxanes: Evidence for the anomeric effect from X-ray crystal structure analysis

The molecular structures of 2,2-di(para-substituted phenyl)-1,3-dioxanes were elucidated for the first time by X-ray crystallographic analysis, which revealed two important structural features: (1) These compounds have the chair conformation in which electron-withdrawing aryl groups [viz. p-nitro-or p-(trifluormethyl)phenyl] are always axial and electron-donating aryl groups (viz. p-methoxyphenyl) are always equatorial. (2) In these compounds as well as in symmetrically substituted 2,2-diphenyl-1,3-dioxane the axial C2-aryl bond is longer than the equatorial C2-aryl bond. The axial preference of the electron-withdrawing aryl group was also demonstrated in solution by 1H and 13C NMR spectroscopy. The anomeric carbon substituted with an electron-withdrawing aryl group resonates at an unusually high field, as does the aromatic carbon bearing the electron-withdrawing substituent. The observed 13C NMR data clearly indicate enhanced electron density at these carbons due to the anomeric effect. Semiempirical molecular orbital calculations by the MOPAK PM3 method reproduced the bond lengthening for axial C2-aryl, while the heat of formation derived from this calculation failed to support the axial preference of electron-withdrawing aryl groups. The X-ray crystallographic data on the conformational preference and bond lengths at the anomeric carbon, as well as the solution NMR spectroscopic data, clearly indicate the anomeric effect that is best rationalized in terms of stabilizing interaction between the lone-pair electrons on the ring oxygens and the antibonding orbital of the axial C2-aryl bond.

Dirhodium-Catalyzed Enantioselective B?H Bond Insertion of gem-Diaryl Carbenes: Efficient Access to gem-Diarylmethine Boranes

The scarcity of reliable methods for synthesizing chiral gem-diarylmethine borons limits their applications. Herein, we report a method for highly enantioselective dirhodium-catalyzed B?H bond insertion reactions with diaryl diazomethanes as carbene precursors. These reactions afforded chiral gem-diarylmethine borane compounds in high yield (up to 99 % yield), high activity (turnover numbers up to 14 300), high enantioselectivity (up to 99 % ee) and showed unprecedented broad functional group tolerance. The borane compounds synthesized by this method could be efficiently transformed into diaryl methanol, diaryl methyl amine, and triaryl methane derivatives with good stereospecificity. Mechanistic studies suggested that the borane adduct coordinated to the rhodium catalyst and thus interfered with decomposition of the diazomethane, and that insertion of a rhodium carbene (generated from the diaryl diazomethane) into the B?H bond was most likely the rate-determining step.

Systematic Evaluation of 1,2-Migratory Aptitude in Alkylidene Carbenes

Alkylidene carbenes undergo rapid inter- and intramolecular reactions and rearrangements, including 1,2-migrations of β-substituents to generate alkynes. Their propensity for substituent migration exerts profound influence over the broader utility of alkylidene carbene intermediates, yet prior efforts to categorize 1,2-migratory aptitude in these elusive species have been hampered by disparate modes of carbene generation, ultrashort carbene lifetimes, mechanistic ambiguities, and the need to individually prepare a series of 13C-labeled precursors. Herein we report on the rearrangement of 13C-alkylidene carbenes generated in situ by the homologation of carbonyl compounds with [13C]-Li-TMS-diazomethane, an approach that obviates the need for isotopically labeled substrates and has expedited a systematic investigation (13C{1H} NMR, DLPNO-CCSD(T)) of migratory aptitudes in an unprecedented range of more than 30 alkylidene carbenes. Hammett analyses of the reactions of 26 differentially substituted benzophenones reveal several counterintuitive features of 1,2-migration in alkylidene carbenes that may prove of utility in the study and synthetic application of unsaturated carbenes more generally.

A convenient pinacol coupling of diaryl ketones with B2pin2viapyridine catalysis

A convenient, pyridine-boryl radical-mediated pinacol coupling of diaryl ketones is developed. In contrast to the conventional pinacol coupling that requires sensitive reducing metal, the current method employs a stable diboron reagent and pyridine Lewis base catalyst for the generation of a ketyl radical. The newly developed process is operationally simple, and the desired diols are produced with excellent efficiency in up to 99% yield within 1 hour. The superior reactivity of diaryl ketone was observed over monoaryl carbonyl compounds and analyzed by DFT calculations, which suggests the necessity of both aromatic rings for the maximum stabilization of the transition states.

Water Phase, Room Temperature, Ligand-Free Suzuki–Miyaura Cross-Coupling: A Green Gateway to Aryl Ketones by C–N Bond Cleavage

We report herein a green strategy for synthesis of aryl ketones from twisted amides by using Pd(OAc)2 as catalysts. This method shows high functional group tolerance to offer a variety of ketones in good yields under mild conditions (up to 94 %). Notably, this methodology demonstrates the first water phase, room temperature, ligand-free Suzuki–Miyaura coupling through C–N bond cleavage, which is environmentally friendly and might facilitate the development of amide based green chemistry.

Photocontrolled Radical Polymerization from Hydridic C-H Bonds

Given the ubiquity of carbon-hydrogen bonds in biomolecules and polymer backbones, the development of a photocontrolled polymerization selectively grafting from a C-H bond represents a powerful strategy for polymer conjugation. This approach would circumvent the need for complex synthetic pathways currently used to introduce functionality at a polymer chain end. On this basis, we developed a hydrogen-atom abstraction strategy that allows for a controlled polymerization selectively from a hydridic C-H bond using a benzophenone photocatalyst, a trithiocarbonate-derived disulfide, and visible light. We performed the polymerization from a variety of ethers, alkanes, unactivated C-H bonds, and alcohols. Our method lends itself to photocontrol which has important implications for building advanced macromolecular architectures. Finally, we demonstrate that we can graft polymer chains controllably from poly(ethylene glycol) showcasing the potential application of this method for controlled grafting from C-H bonds of commodity polymers.

Binuclear Palladium Complex Immobilized on Mesoporous SBA-16: Efficient Heterogeneous Catalyst for the Carbonylative Suzuki Coupling Reaction of Aryl Iodides and Arylboronic Acids Using Cr(CO)6 as Carbonyl Source

Abstract: In this study, a binuclear palladium complex immobilized on the organo-functionalized SBA-16 was prepared and structurally characterized by routine techniques. Characterizations indicated that the mesostructure of SBA-16 was maintained after the immobilization of palladium complex. Then, the prepared nanomaterial was applied as a heterogeneous catalyst in the carbonylative Suzuki coupling reaction of aryl iodides with arylboronic acids using Cr(CO)6 as carbonyl source. The catalyst was efficiently promoted the coupling reactions of various aryl iodides and arylboronic acids to give the corresponding diaryl ketones in excellent yields. Moreover, the catalyst was readily recovered by filtration and could be reused for seven cycles without losing its structural integrity and catalytic activity. Graphic Abstract: [Figure not available: see fulltext.].

Kinetically Controlled, Highly Chemoselective Acylation of Functionalized Grignard Reagents with Amides by N?C Cleavage

The direct transition-metal-free acylation of amides with functionalized Grignard reagents by highly chemoselective N?C cleavage under kinetic control has been accomplished. The method offers rapid and convergent access to functionalized biaryl ketones through transient tetrahedral intermediates. The direct access to functionalized Grignard reagents by in situ halogen–magnesium exchange promoted by the versatile turbo-Grignard reagent (iPrMgCl?LiCl) permits excellent substrate scope with respect to both the amide and Grignard coupling partners. These reactions enable facile, operationally simple and chemoselective access to tetrahedral intermediates from amides under significantly milder conditions than chelation-controlled intermediates. This novel direct two-component coupling sets the stage for using amides as acylating reagents in an alternative paradigm to the metal-chelated approach, acyl metals and Weinreb amides.

Direct C-H Arylation of Aldehydes by Merging Photocatalyzed Hydrogen Atom Transfer with Palladium Catalysis

Herein, we report that merging palladium catalysis with hydrogen atom transfer (HAT) photocatalysis enabled direct arylations and alkenylations of aldehyde C-H bonds, facilitating visible light-catalyzed construction of a variety of ketones. Tetrabutylammonium decatungstate and anthraquinone were found to act as synergistic HAT photocatalysts. Density functional theory calculations suggested a Pd0-PdII-PdIII-PdI-Pd0 pathway and revealed that regeneration of the Pd0 catalyst and the photocatalyst occurs simultaneously in the presence of KHCO3. This regeneration features a low energy barrier, promoting efficient coupling of the palladium catalytic cycle with the photocatalytic cycle. The work reported herein suggests great promise for further applications of HAT photocatalysis in palladium-catalyzed cross-coupling and C-H functionalization reactions to be successful.

I-Pr2NMgCl·LiCl Enables the Synthesis of Ketones by Direct Addition of Grignard Reagents to Carboxylate Anions

The direct preparation of ketones from carboxylate anions is greatly limited by the required use of organolithium reagents or activated acyl sources that need to be independently prepared. Herein, a specific magnesium amide additive is used to activate and control the addition of more tolerant Grignard reagents to carboxylate anions. This strategy enables the modular synthesis of ketones from CO2 and the preparation of isotopically labeled pharmaceutical building blocks in a single operation.