191019-76-8

Upstream product

• 873-73-4 4-n-chlorophenylacetylene 
• 76-02-8 trifluoroacetyl chloride 
• 104-88-1 4-chlorobenzaldehyde 
• 1073-67-2 4-vinylbenzyl chloride 
• 4591-28-0 dichloroketene 

Downstream Products

• 152714-07-3 3-(4-chlorophenyl)cyclobutanone 
• 26717-54-4 β-(4-chlorophenyl)-γ-butyrolactone 
• 89359-16-0 (S)-β-(4-chlorophenyl)-γ-butyrolactone 
• 147224-51-9 β-(R)-(p-chlorophenyl)-γ-butyrolactone 
• 245662-60-6 1-[(3S)-3-(4-chlorophenyl)cyclobut-1-enyloxyl]-1,1-diethyl-1-silapropane 
• 69308-37-8 (R)-baclofen 
• 70206-22-3 Baclofen hydrochloride 
• 22518-27-0 4-(4-chlorophenyl)pyrrolidin-2-one 
• 718599-07-6 4,4-dichloro-3-(4-chloro-phenyl)-N-isopropyl-butyramide 

Relevant academic research and scientific papers

Copper-Catalyzed Sulfonylation of Cyclobutanone Oxime Esters with Sulfonyl Hydrazides

A copper-catalyzed radical cross-coupling of cyclobutanone oxime esters with sulfonyl hydrazides has been developed. The copper-based catalytic system proved crucial for cleavage of the C-C bond of cyclobutanone oximes and for selective C-S bond-formation involving persistent sulfonyl-metal radical intermediates. This protocol is distinguished by the low-cost catalytic system, which does not require ligand, base, or toxic cyanide salt, and by the use of readily accessible starting materials, as well as broad substrate scope, providing an efficient approach to various diversely substituted cyano-containing sulfones.

Manganese=Catalyzed Achmatowicz Rearrangement Using Green Oxidant H2O2

Oxidation reactions have been extensively studied in the context of the transformations of biomass=derived furans. However, in contrast to the vast literature on utilizing the stoichiometric oxidants, such as m=CPBA and NBS, catalytic methods for the oxidative furan=recyclizations remain scarcely investigated. Given this, we report a means of manganese=catalyzed oxidations of furan with low loading, achieving the Achmatowicz rearrangement in the presence of hydrogen peroxide as an environmentally benign oxidant under mild conditions with wide functional group compatibility.

Synthesis of Silylated Cyclobutanone and Cyclobutene Derivatives Involving 1,4-Addition of Zinc-Based Silicon Nucleophiles

A copper-catalyzed conjugate silylation of various cyclobutenone derivatives with Me2PhSiZnCl ? 2LiCl or (Me2PhSi)2Zn ? xLiCl (x≤4) to generate β-silylated cyclobutanones is reported. Trapping the intermediate enolate with ClP(O)(OPh)2 affords silylated enol phosphates that can be further engaged in Kumada cross-coupling reactions to yield silylated cyclobutene derivatives.

Photoinduced, Copper-Catalyzed Three-Component Annulation of gem-Dialkylthio Enynes

Photoinduced, copper-catalyzed three-component radical annulation of gem-dialkylthio enynes, cyclobutanone oxime esters, and boronic acids was achieved, forming highly functionalized aryl thienyl sulfides with both good chemo- and diastereoselectivities. The reaction proceeds through a domino sequence involving cyanoalkyl radical-mediated intramolecular annulation of gem-dialkylthio enyne, alkenyl radical-promoted C(sp3)-S bond cleavage, and sulfur-centered radical-trapped Cu(II)-facilitated C-S cross-coupling. The protocol features simultaneous establishment of cyanoalkyl, cyclopentanone, and thiophene moieties and a thioether C-S bond in one pot with broad substrate scopes and versatile functional group tolerance under mild conditions.

Copper-catalyzed ring-opening C(sp3)-N coupling of cycloketone oxime esters: Access to 1°, 2° and 3° alkyl amines

A novel copper-catalyzed C(sp3)-N coupling of cycloketone oxime esters with nitrogen nucleophiles has been realized. All of the N-aryl/alkylanilines, anilines and benzophenone imine could be employed in this protocol to produce a variety of 1°, 2° and 3° alkyl amines in one or two steps. These resultant cyano-containing alkyl amines were proven to be versatile synthetic building blocks in a variety of chemical transformations.

Transition-Metal-Promoted Direct C?H Cyanoalkylation and Cyanoalkoxylation of Internal Alkenes via Radical C?C Bond Cleavage of Cycloketone Oxime Esters

Transition-metal-catalyzed alkyl-Heck-type cross-coupling of olefinic C?H bonds has been a challenge in the C?H activation area. Herein, we report FeCl3-promoted efficient direct C?H cyanoalkylation of internal alkenes, that is, ketene dithioacetals, with cycloketone oxime esters via radical C?C bond cleavage under the redox-neutral conditions. With CuCl2 as the catalyst under a dioxygen atmosphere direct C?H cyanoalkoxylation of the same internal alkenes was achieved. The cyanoalkylated tetrasubstituted alkene products could be diversely transformed to cyanoalkyl-funtionalized N- and S-heterocyclic compounds. The mechanistic studies have revealed that these C?H cyanoalkylation and cyanoalkoxylation reactions proceed through a radical pathway. (Figure presented.).

Baeyer-Villiger Oxidation of Cyclobutanones with 10-Methylacridinium as an Efficient Organocatalyst

Baeyer-Villiger oxidation of cyclobutanones is achieved in current developed protocol with 10-methylacridinium perchlorate (AcrH +ClO4-) as a novel organocatalyst both with irradiation at room temperature and without irradiation at elevated temperature. Excellent yields of the corresponding lactones are obtained and the possible mechanism has been proposed.

Enantioselective baeyer-villiger oxidation: Desymmetrization of meso cyclic ketones and kinetic resolution of racemic 2-arylcyclohexanones

Catalytic enantioselective Baeyer-Villiger (BV) oxidations of racemic and meso cyclic ketones were achieved in the presence of chiral N,N'-dioxide-Sc III complex catalysts. The BV oxidations of prochiral cyclohexanones and cyclobutanones afforded series of optically active μ- and γ-lactones, respectively, in up to 99% yield and 95% ee. Meanwhile, the kinetic resolution of racemic 2-arylcyclohexanones was also realized via an abnormal BV oxidation. Enantioenriched 3-aryloxepan-2-ones, whose formation is counter to the migratory aptitude, were obtained preferentially. Both the lactones and the unreacted ketones were obtained with high ee values.

Enantioselective baeyer-villiger oxidation: Desymmetrization of meso cyclic ketones and kinetic resolution of racemic 2-arylcyclohexanones

Catalytic enantioselective Baeyer-Villiger (BV) oxidations of racemic and meso cyclic ketones were achieved in the presence of chiral N,N'-dioxide-Sc III complex catalysts. The BV oxidations of prochiral cyclohexanones and cyclobutanones afforded series of optically active μ- and γ-lactones, respectively, in up to 99% yield and 95% ee. Meanwhile, the kinetic resolution of racemic 2-arylcyclohexanones was also realized via an abnormal BV oxidation. Enantioenriched 3-aryloxepan-2-ones, whose formation is counter to the migratory aptitude, were obtained preferentially. Both the lactones and the unreacted ketones were obtained with high ee values.