76373-38-1

Upstream product

• 5707-04-0 Phenylselenyl chloride 
• 529-34-0 3,4-dihydronaphthalene-1(2H)-one 
• 1666-13-3 diphenyl diselenide 
• 645-96-5 Benzeneselenol 
• 447-53-0 1,2-Dihydronaphthalene 
• 1056246-70-8 2-bromo-1-tetralone 

Downstream Products

• 104755-23-9 C₁₆H₁₄Cl₂OSe 

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.

Methods for the introduction of a Phenylselenium Dichloride Group into he α-position of Carbonyl Compounds. Syntheses of Enones.

Phenylselenium trichloride, PhSeCl3, direcly introduced, in fair yield, a PhSeCl2 group into the α-position of ketones with loss of HCl.To some extent, depending on the substrate, this reagent was also shown to act as a chlorinating agent toward ketones, yielding α-chloro ketones and α-phenylselenenyl ketones.The latter compounds were readily converted to selenium(IV) dichlorides by SO2Cl2 chlorination to significantly improve the overall yields of the selenetion process.The consecutive treatment of ketones with PhSeCl and SO2Cl2 could also be used for the introduction of a PhSeCl2 group, but this procedure was usually less efficient than the PhSeCl3-based one.Unsymmetrical ketones were selenated with poor regiocontrol.Aldehydes were primarily chlorinated by treatment with PhSeCl3, but consecutive treatment with PhSeCl3 and SO2Cl2 introduced a PhSeCl2 group into the α-position.Carboxylic acids and esters were ureactive toward PhSeCl3 and PhSeCl.PhSeCl3 underwent addition reactions with enones to introduce a PhSeCl2 group α or β to the carbonyl group, depending on the substrate.The carbonyl compounds substituted in the α-position with a PhSeCl2 group were easily converted to the corresponding α,β-unsaturated carbonyl compounds after hydrolysis/selenoxide elimination.Since the selenium(IV) intermediates involved were highly crustalline and easy to purify, the preparation of enones from symmetrical ketones via PhSeCl2 introduction/hydrolytic elimination was especially convenient to perform from the operational point of view.

A FACILE ACCESS TO α-PHENYLSELENENYL CARBONYL COMPOUNDS BY ELECTROCHEMICAL OXIDATION

A novel α-phenylselenenylation of carbonyl compounds has been performed by electrolysis of a solution of ketones, diphenyl diselenide, tetraethyl-ammonium bromide, and magnesium bromide in polar solvents (MeOH, AcOH, MeCN).The electrolysis enables us to p