70090-77-6

Upstream product

• 106-96-7 propargyl bromide 
• 352-13-6 4-flourophenylmagnesium bromide 
• 405-99-2 para-fluorostyrene 
• 127510-50-3 1-(2,2-dibromocyclopropyl)-4-fluorobenzene 
• 766-98-3 1-ethynyl-4-fluorobenzene 
• 50-00-0 formaldehyd 
• 925-90-6 ethylmagnesium bromide 
• 459-57-4 4-fluorobenzaldehyde 
• 460-00-4 1-Bromo-4-fluorobenzene 
• 706-06-9 3-(4-flurophenyl)prop-2-ynoic acid 
• 70090-68-5 1-fluoro-4-(prop-2-yn-1-yl)benzene 
• 75-25-2 Bromoform 

Downstream Products

• 1137228-38-6 (E)-N-(3-(4-fluorophenyl)allyl)aniline 
• 1234935-56-8 (3-(4-fluorophenyl)prop-1-en-2-yl)dimethyl(phenyl)silane 
• 1234935-58-0 2-(dimethylphenylsilyl)-3-(4-fluorophenyl)-2-propene 
• 210840-57-6 Rh(η(3)-CH2CHCHC6H4F-p)(CO)(PPh3)2 
• 206003-21-6 (P(C₂H₅)3)2Rh(Cl)(CH₂CCHC₆H₄F) 
• 206003-24-9 (P(CH₃)3)2Rh(Cl)(CH₂CCHC₆H₄F) 
• 206003-26-1 (P(CH₃)3)2Rh(Cl)(CH₂CCHC₆H₄F) 
• 206003-28-3 (P(CH₃)3)3Rh(Cl)(CH₂CCHC₆H₄F) 

Relevant academic research and scientific papers

Indene formation upon borane-induced cyclization of arylallenes, 1,1-carboboration, and retro-hydroboration

We herein report the reaction of arylallenes with tris(pentafluorophenyl)borane that yields pentafluorophenyl substituted indenes. The tris(pentafluorophenyl)borane induces the cyclization of the allene and transfers a pentafluorophenyl ring in the course of this reaction. A Hammett plot analysis and DFT computations indicate a 1,1-carboboration to be the C-C bond-forming step.

Polymerization of Allenes by Using an Iron(II) β-Diketiminate Pre-Catalyst to Generate High Mn Polymers

Herein, we report an iron(II)-catalyzed polymerization of arylallenes. This reaction proceeds rapidly at room temperature in the presence of a hydride co-catalyst to generate polymers of weight up to Mn=189 000 Da. We have determined the polymer structure and chain length for a range of monomers through a combination of NMR, differential scanning calorimetry (DSC) and gel permeation chromatography (GPC) analysis. Mechanistically, we postulate that the co-catalyst does not react to form an iron(II) hydride in situ, but instead the chain growth is proceeding via a reactive Fe(III) species. We have also performed kinetic and isotopic experiments to further our understanding. The formation of a highly unusual 1,3-substituted cyclobutane side-product is also investigated.

Copper(ii)-catalyzed protoboration of allenes in aqueous media and open air

A method has been developed for the facile Cu(ii)-catalyzed protoboration of monosubstituted allenes in aqueous media under atmospheric conditions. The reaction occurs site selectively, favoring internal alkene protoboration to afford 1,1-disubstituted vinylboronic acid derivatives (up to 93?:?7) with modest to good yields. The method has been applied to a variety of phenylallene derivatives as well as alkyl-substituted allenes. This journal is

Photoredox-Catalyzed α-Aminoalkylcarboxylation of Allenes with CO2

The photoredox-catalyzed α-aminoalkylcarboxylation of aryl allenes with CO2 and N,N-dimethylanilines is reported for the first time (26 examples, up to 96% yield). In the case of electron-deficient allenes, good regioselectivity was observed (up to 94:6), exclusively generating kinetic products over thermodynamic products. This protocol is a novel synthetic method for highly functionalized β,γ-unsaturated γ-aminobutyric esters.

Trifluoromethylation of Allenes: An Expedient Access to α-Trifluoromethylated Enones at Room Temperature

A silver(I) catalyzed regioselective trifluoromethylation of allenes using Langlois's salt (NaOSOCF3) is demonstrated. This transformation enables direct expedient access to α-trifluoromethylated acroleins, which are valuable synthons for a number of pharmaceuticals and agrochemicals containing vinyl-CF3 moieties. Versatility of this trifluoromethylation method has been established with good yield and excellent regioselectivity. Preliminary experiments and computational studies were carried out to elucidate the mechanistic insight of this protocol.

Palladium-Catalyzed Oxidative Carbonylative Coupling of Arylallenes, Arylboronic Acids, and Nitroarenes

In this Letter, a palladium-catalyzed multicomponent procedure for the selective synthesis of α-substituted α,β-unsaturated ketones has been developed. With readily available allenes, arylboronic acids, and nitroarenes as the substrates, the reaction proceeds selectively to the desired α-substituted enones. Notably, no manipulation of carbon monoxide gas is needed here, and Mo(CO)6 has been applied as a stable solid CO source instead. Additionally, as an oxidative coupling reaction, nitroarenes are used as both the amine source and the oxidant to regenerate the active palladium species.

Borane-Induced Dimerization of Arylallenes

A series of arylallenes react with HB(C6F5)2 in a 2:1 molar ratio to give the tail-to-tail 1,6-diaryl-2-boryl-hexa-1,5-diene coupling products. The reaction of the phenylallene substrate with HB(C6F5)

Fluorinative Rearrangements of Substituted Phenylallenes Mediated by (Difluoroiodo)toluene: Synthesis of α-(Difluoromethyl)styrenes

Phenylallenes undergo fluorinative rearrangement upon the action of (difluoroiodo)toluene in the presence of 20 mol % BF3?OEt2 to yield α-difluoromethyl styrenes. This unprecedented reaction was entirely chemoselective for the internal allene π bond, and showed remarkable regioselectivity during the fluorination event. Substituted phenylallenes, phenylallenes possessing both phenyl- and α-allenyl substituents, and diphenylallenes were investigated, and good functional-group compatibility was observed throughout. The ease with which allenes can be prepared on a large scale, and the operational simplicity of this reaction allowed us to rapidly access fluorine-containing building blocks that have not been accessed by conventional deoxyfluorination strategies.

Highly 2,3-Selective Polymerization of Phenylallene and Its Derivatives with Rare-Earth Metal Catalysts: From Amorphous to Crystalline Products

Rare-earth metal complexes (Flu-CH2-Py)Ln(CH2SiMe3)2(THF)n (Ln=Sc(1), Lu(2), Tm(3), Y(4) and Gd(5)), upon the activation of [Ph3C][B(C6F5)4] and AliBu3, were employed to catalyze the polymerization of allene derivatives under mild conditions. The Gd, Y, Tm, Lu metal based precursors exhibited distinguished 2,3-selectivity (>99.9 %) for phenylallene (PA) polymerization, whereas the smallest Sc metal based precursor showed a moderate 2,3-selectivity. The activity increased with the central metal size following the trend of Gd(5)>Tm(4)>Y(3)>Lu(2)>Sc(1). Moreover, Gd(5) also realized the purely 2,3-selective polymerizations of polar or nonpolar allene derivatives, para-methylphenylallene, para-flourophenylallene and para-methoxyphenylallene, regardless of electron-donating or -withdrawing substituents. Owing to the highly regular backbones, these polymers (except PPA) were crystalline, thus being the first crystalline polymers based on allene derivatives.

Synthesis of Terminal Allenes via a Copper-Catalyzed Decarboxylative Coupling Reaction of Alkynyl Carboxylic Acids

Synthesis of terminal allenes via a copper-catalyzed decarboxylative coupling reaction was developed. Aryl alkynyl carboxylic acid, paraformaldehyde, and dicyclohexylamine were reacted with CuI (20 mol %) in diglyme at 100°C for 2 h to produce the terminal allene in moderate to good yields. The method showed good functional group tolerance.