2749-98-6

Upstream product

• 104-88-1 4-chlorobenzaldehyde 
• 1073-67-2 4-vinylbenzyl chloride 
• 75-25-2 Bromoform 
• 873-77-8 (4-chlorphenyl)magnesium bromide 
• 106-96-7 propargyl bromide 
• 38365-51-4 1,1-dibromo-2-(4-chlorophenyl)cyclopropane 
• 925-90-6 ethylmagnesium bromide 
• 106-39-8 bromochlorobenzene 
• 50-00-0 formaldehyd 
• 3240-10-6 (4-chlorophenyl)propiolic acid 
• 70090-69-6 1-chloro-4-(prop-2-yn-1-yl)benzene 
• 637-87-6 1-Chloro-4-iodobenzene 
• 29805-11-6 1-(4-chlorophenyl)prop-2-yn-1-ol 
• 53915-69-8 allenyltributylstannane 

Downstream Products

• 1039513-51-3 (E)-3-(4-chlorobenzyl)-4-(4-chlorobenzylidene)cyclopent-2-enone 
• 1039513-55-7 (E)-3-(4-chlorobenzyl)-5-(4-chlorobenzylidene)cyclopent-2-enone 
• 1187852-59-0 C₁₈H₁₄BrClO₂ 
• 1234935-61-5 2-(dimethylphenylsilyl)-3-(4-chlorophenyl)-2-propene 
• 1234935-59-1 (3-(4-chlorophenyl)prop-1-en-2-yl)dimethyl(phenyl)silane 
• 1446696-23-6 4,4,5,5-tetramethyl-2-[(2E)-3-(4-chlorophenyl)prop-2-en-1-yl]-1,3,2-dioxaborolane 
• 1616487-58-1 C₁₅H₁₆ClNO₅ 
• 1616487-64-9 C₁₅H₁₆ClNO₅ 

Relevant academic research and scientific papers

Photoredox Catalyzed Sulfonylation of Multisubstituted Allenes with Ru(bpy)3Cl2 or Rhodamine B

A highly regio- and stereoselective sulfonylation of allenes was developed that provided direct access to α, β-substituted unsaturated sulfone. By means of visible-light photoredox catalysis, the free radicals produced by p-toluenesulfonic acid reacted with multisubstituted allenes to obtain Markovnikov-type vinyl sulfones with Ru(bpy)3Cl2 or Rhodamine B as photocatalyst. The yield of this reaction could reach up to 91%. A series of unsaturated sulfones would be used for further transformation to some valuable compounds.

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.

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.

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

Intermolecular Allene Functionalization by Silver-Nitrene Catalysis

Under silver catalysis conditions, using [Tp*,BrAg]2 as the catalyst precursor, allenes react with PhI═NTs in the first example of efficient metal-mediated intermolecular nitrene transfer to such substrates. The nature of the substituent at the allene seems crucial for the reaction outcome since arylallenes are converted into azetidine derivatives, whereas methylene aziridines are the products resulting from alkylallenes. Mechanistic studies allow proposing that azetidines are formed through unstable cyclopropylimine intermediates, which further incorporate a second nitrene group, both processes being silver-mediated. Methylene aziridines from alkylallenes derive from catalytic nitrene addition to the allene double bonds. Both routes have resulted to be productive for further synthetic transformations affording aminocyclopropanes.

Formation of Nucleophilic Allylboranes from Molecular Hydrogen and Allenes Catalyzed by a Pyridonate Borane that Displays Frustrated Lewis Pair Reactivity

Here we report the in situ generation of nucleophilic allylboranes from H2 and allenes mediated by a pyridonate borane that displays frustrated-Lewis-pair reactivity. Experimental and computational mechanistic investigations reveal that upon H2 activation, the covalently bound pyridonate substituent becomes a datively bound pyridone ligand. Dissociation of the formed pyridone borane complex liberates Piers borane and enables a hydroboration of the allene. The allylboranes generated in this way are reactive towards nitriles. A catalytic protocol for the formation of allylboranes from H2 and allenes and the allylation of nitriles has been devised. This catalytic reaction is a conceptually new way to use molecular H2 in organic synthesis.

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.

Enantioselective Copper-Catalyzed Three-Component Carboboronation of Allenes: Access to Functionalized Dibenzo [b,f][1,4]oxazepine Derivatives

A copper-catalyzed enantioselective three-component difunctionalization of allenes with seven-membered cyclic imines and bis(pinacolato)diboron (B2(Pin)2) to approach functionalized dibenzo[b,f][1,4]oxazepine derivatives is developed. The chiral products are obtained in up to 81% yield, >20:1 dr, and 98% ee when either a chiral diphosphine ligand or a chiral ferrocenyl-based P,N-ligand is used. Furthermore, the reaction exhibits reversed diastereoselectivities when the chiral diphosphine ligand and the chiral P,N-ligand are used respectively. (Figure presented.).

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.