83756-35-8

Upstream product

• 104755-17-1 C₁₂H₁₀Cl₂OSSe 
• 10531-41-6 2-Bromoacetylthiophene 
• 1666-13-3 diphenyl diselenide 
• 645-96-5 Benzeneselenol 
• 1918-82-7 2-vinylthiophene 
• 20343-90-2 bis(phenylseleno)methane 
• 229970-94-9 N‐methoxy‐N‐methyl‐2‐thiophenecarboxamide 
• 42572-42-9 phenylselenium trichloride 
• 88-15-3 2-Acetylthiophene 
• 186581-53-3 diazomethane 
• 76529-36-7 Se-phenyl thiophene-2-carboselenoate 

Downstream Products

• 88-15-3 2-Acetylthiophene 
• 1218948-26-5 C₁₅H₁₅NSSe 

Relevant academic research and scientific papers

Acridine Orange Hemi(Zinc Chloride) Salt as a Lewis Acid-Photoredox Hybrid Catalyst for the Generation of α-Carbonyl Radicals

A readily accessible organic-inorganic hybrid catalyst is reported for the reductive fragmentation of α-halocarbonyl compounds. The robust hybrid catalyst is a self-stabilizing combination of ZnCl2 Lewis acid and acridine orange as the photoactive organic dye. Mechanistic specifics of this hybrid catalyst have been studied in detail using both photophysical and electrochemical experiments. A systematic study enabled the discovery of the appropriate Lewis acid for the effective LUMO stabilization of α-halocarbonyl compounds and thereby lowering of reduction potential within the range of a standard organic dye. This strategy resolves the issues like dehalogenative hydrogenation or homo-coupling of alkyl radicals by guiding the photoredox cycle through an oxidative quenching pathway. The cooperativity between the photoactive organic dye and the Lewis acid counterparts empowers functionalization with a wide range of coupling partners through efficient and controlled generation of alkyl radicals and serves as an appropriate alternative to the expensive late transition metal-based photocatalysts. To demonstrate the application potential of this cooperative catalytic system, four different synthetic transformations of α-carbonyl bromides were explored with broad substrate scopes.

Visible-light-induced oxidative coupling of vinylarenes with diselenides leading to α-aryl and α-alkyl selenomethyl ketones

A visible-light-induced oxidative coupling of diselenides with readily available vinylarenes is demonstrated. This benign protocol allows one to access a wide range of α-aryl and α-alkyl selenomethyl ketones in good yields with excellent functional group compatibility. The distinct advantages of this protocol over all previous methods include the use of a green solvent and air as an oxidant and the lack of a photocatalyst, a base, and an oxidant as well as better green chemistry matrices. Furthermore, the title reaction can be performed with natural sunlight, the most sustainable energy source imaginable. Additionally, the mild reaction conditions, easy operation and suitability for the modification of styrene-functionalized biomolecules make the current reaction system a more attractive method for the synthesis of a variety of medicinal and agrochemical compounds of interest.

Visible light promoted alpha-selenoketone compound synthesis method

The invention discloses a visible light promoted alpha-selenoketone compound synthesis method. The method comprises the following steps: A, sequentially adding compounds 1 and 2 into a reactor under an open condition; B, carrying out stirring reaction under a certain temperature condition and light source irradiation; C, after the reaction is finished, evaporating the solvent under reduced pressure to obtain a crude product; and D, carrying out column chromatography purification to obtain alpha-selenoketone 3. According to the preparation method, olefin and diselenide are used as the raw materials, one of acetonitrile, dichloromethane and ethyl acetate is used as a solvent, the reaction temperature is room temperature, the alpha-selenoketone compound is efficiently synthesized under irradiation of a white fluorescence light source, and compared with a traditional synthesis method, the method has the advantages that the reaction condition is mild, and the method can be smoothly carriedout at room temperature; the operation is simple, and all operations can be carried out in an open system; meanwhile, the method avoids using expensive transition metal catalysts, and has the characteristics of economy, green and environmental protection and the like.

Expeditious and Chemoselective Synthesis of α-Aryl and α-Alkyl Selenomethylketones via Homologation Chemistry

Diselenoacetals, previously considered byproducts in homologation tactics en route to α-selenoketones, are herein found to be excellent starting materials for this purpose. The easy selenium/lithium exchange they undergo affords seleno carbanions which are smoothly added to Weinreb amides to chemoselectively prepare α-aryl- and α-alkyl seleno methylketones through a single chemical operation. No racemization events are observed in the presence of optically pure starting materials.

A radical cyclization route to cyclic imines

A novel route to cyclic imines based on 5-exo radical cyclization is explored. The radical precursors are imines prepared from allylamine and readily available α-phenylselenenyl ketones.

PHENYL SELENIUM TRICHLORIDE IN SYNTHESIS. REACTION WITH KETONES. A NEW VARIATION OF THE SELENOXIDE ELIMINATION REACTION

Phenyl selenium trichloride was used for the introduction of a PhSeCl2-group into the α-position of ketones.These products were converted to enones (hydrolysis/selenoxide elimination) or α-phenylselenoketones (thiourea-reduction).

REACTION OF DIAZOMETHANE WITH SELENOESTERS PREPARATION OF α-(ALKYL- OR ARYLSELENO)METHYL KETONES AND METHYL KETONES

The reaction of diazomethane with a series of selenoesters 1 in the presence of CuI, CuSePh or Cu powder produced α-(alkyl- or arylseleno)methyl ketones 2 in yield of 41-65percent.Methyl ketones 3 and bis(arylseleno)methanes 9 or 14 were formed as by-products.The direct conversion of selenoesters to methyl ketones was accomplished in high yield by the usual reaction with diazomethane, followed by workup with HBr solution.The simultaneous copper-catalyzed reactions of selenoesters 1c and 1i with diazomethane resulted in crossover, with the formation of all four possible α-seleno ketones 2b, 2c, 2h and 2i.A non-concerted mechanism involving attack by the diazo compound upon the acyl carbon atom of an activated selenoester with the formation of a tetrahedral intermediate 11 has been suggested.The reaction of the selenothiocarbamate 4 with diazomethane resulted in 1,3-dipolar cycloaddition to afford 5 instead of insertion into the acyl-selenium bond.

HOMOLOGATION OF SELENOESTERS TO (PHENYLSELENO)- OR (METHYLSELENO)METHYL KETONES WITH DIAZOMETHANE

The copper or cuprous iodide-catalyzed insertion of diazomethane into the acylselenium linkage of selenoesters 1a- 1f and selenocarbonate 1g afforded the corresponding ketones 2a- 2f and the ester 2g, respectively, as the chief products.