133708-82-4

Upstream product

• 6996-92-5 benzeneseleninic acid 
• 64-19-7 acetic acid 
• 110-83-8 cyclohexene 
• 1666-13-3 diphenyl diselenide 
• 3240-34-4 [bis(acetoxy)iodo]benzene 
• 2179-79-5 phenyl selenocyanate 
• 546-67-8 lead(IV) tetraacetate 
• 133708-80-2 benzeneselenenyl m-nitrobenzenesulfonate 

Downstream Products

• 5837-71-8 (±)-cis-2-bromocyclohexyl acetate 
• 33815-66-6 cis-2-chlorocyclohexyl acetate 

Relevant academic research and scientific papers

Novel and convenient acetoxyselenenylation of alkenes catalyzed by potassium iodide

With KI as catalyst and m-chloroperbenzoic acid as the oxidant in acetic acid, a novel and efficient catalytic procedure has been developed for acetoxyselenenylation of alkenes, which providing a series of 2-acetoxy-1-selenenylation compounds with high regioselectivity and good yields in mild conditions. In this protocol, KI is first oxidized by m-chloroperbenzoic acid into acetylhypoiodite, which rapidly reacts with diselenide to form the active electrophilic selenenylating reagent, following an electrophilic addition of alkenes and 2-acetoxy-1-selenenylation compounds are obtained. The suitable equivalent ratio of alkene to diselenide is 1.2.

Iodine-mediated acyloxyselenenylation of alkenes

In the presence of I2, an acyloxyselenenylation of alkenes with diselenides and carboxylic acids is developed. This metal-free iodine-mediated acyloxyselenenylation proceeds efficiently under mild reaction conditions, affording a series of 2-acyloxy-1-selenides with high regioselectivity and in moderate to good yields.

PhI Catalyzed Acetoxyselenylation and Formyloxyselenylation of Alkenes

With PhI as catalyst and mCPBA as oxidant, a novel and efficient catalytic procedure has been developed for the acetoxyselenylation and formyloxyselenylation of alkenes. In this protocol, PhI is first oxidized into hypervalent iodine intermediate, which promotes the cleavage of Se–Se bond in diselenides. The in?situ generated electrophilic selenium species then reacts with alkenes, affording 2-acetoxy-1-selenides and 2-formyloxy-1-selenides in high regioselectivity and good yields.

Acidic hierarchical zeolite ZSM-5 supported Ru catalyst with high activity and selectivity in the seleno-functionalization of alkenes

The acidic hierarchical zeolite ZSM-5 (HZSM-5-H) was synthesized for the preparation of a supported Ru catalyst (Ru/HZSM-5-H). The obtained Ru/HZSM-5-H catalyst shows high activity and product selectivity in the seleno-functionalization of alkenes compared to γ-Al2O3, basic ETS-10 and acidic microporous zeolite ZSM-5 supported Ru catalysts (Ru/γ-Al2O3, Ru/ETS-10 and Ru/HZSM-5, respectively), as well as a homogeneous RuCl3 catalyst. The relatively strong acidic sites in Ru/HZSM-5-H could benefit the adsorption of styrenes and the activation of the CC bond. Meanwhile, Ru4+ in Ru/HZSM-5-H could facilitate the formation of electrophilic selenium species as compared to Ru0 species. In addition, the Ru/HZSM-5-M catalyst exhibits broad substrate compatibility in the difunctionalization of alkenes.

Novel and convenient acetoxyselenenylation of alkenes catalyzed by potassium iodide

With KI as catalyst and m-chloroperbenzoic acid as the oxidant in acetic acid, a novel and efficient catalytic procedure has been developed for acetoxyselenenylation of alkenes, which providing a series of 2-acetoxy-1-selenenylation compounds with high regioselectivity and good yields in mild conditions. In this protocol, KI is first oxidized by m-chloroperbenzoic acid into acetylhypoiodite, which rapidly reacts with diselenide to form the active electrophilic selenenylating reagent, following an electrophilic addition of alkenes and 2-acetoxy-1-selenenylation compounds are obtained. The suitable equivalent ratio of alkene to diselenide is 1.2.

Anti-Markovnikov acetoxyphenylselenation of terminal alkenes

Unexpected anti-Markovnikov acetoxyphenylselenation of terminal alkenes has been achieved by reaction of these substrates with diphenyl diselenide and lead tetraacetate in benzene under thermal conditions (80°C). The corresponding products, 1-acetoxy-2-phenylselenylhydrocarbons accompanied by their isomers, 2-acetoxy-1-phenylselenilhydrocarbons are obtained in moderate to good yields. Acetoxyphenylselenation with same reagents, but in acetic acid as the solvent, yields only expected Markovnikov products.

Iodosobenzene diacetate and diphenyl diselenide: An electrophilic selenenylating agent of double bonds

Phenylseleno-acetoxylation, hydroxylation, etherification and lactonization products are obtained in good yields from the reaction of alkenes with diphenyl diselenide and iodosobenzene diacetate, in acetonitrile.

Oxidative Cleavage of Diselenide by m-Nitrobenzenesulfonyl Peroxide. Novel Method for the Electrophilic Benzeneselenenylations of Olefins and Aromatic Rings

Diphenyl diselenide was found to be readily converted into benzeneselenenyl-m-nitrobenzenesulfonate (PhSeOSO2C6H4NO2-m) by treating with m-nitrobenzenesulfonyl peroxide.When the selenenyl sulfonate thus formed was allowed to react in situ with olefins, such as cyclohexene, 1-octene, or styrene, in the presence of various nucleophiles, the adducts of benzeneselenenyl group and a nucleophile were obtained.As the nucleophiles water, methanol, acetic acid, phenol, and anisole could be employed; oxyselenenylated : R=H, Me, Ac, and Ph) and arylselenenylated : R=H and Me) adducts were afforded.Phenol gave oxyselenenylated products in cyclohexene or 1-octene and arylselenenylated products in styrene.Efficient intramolecular cyclizations of unsaturated alcohols and carboxylic acids were similarly performed by the selenenyl sulfonate to afford corresponding benzeneselenenylated cyclic ethers and lactones.The selenenyl sulfonate was also found to be a highly reactive benzeneselenenylating reagent for aromatic rings, such as anisole, phenol, acetanilide, toluene, and benzene.

Facile Oxyselenation of Olefins in the Presence of Copper(II) or Copper(I) Chloride as Catalyst

Treatment of olefinic hydrocarbons with phenyl selenocyanate in alcohol in the presence of copper(II) or copper(I) chloride affords β-alkoxyalkyl phenyl selenide in good yield.Similar reactions in aqueous tetrahydrofuran or acetic acid-chloroform give the corresponding selenide.The reaction is trans stereospecific in the cases of trans-2-butene, cis-2-butene, and cyclohexene and regiospecific in the cases of styrene, acrylaldehyde, crotonaldehyde, and vinylacetate, respectively.The reaction proceeds even with a catalytic amount of copper(II) chloride.Of the various transition-metal salts examined, nickel(II) halides are similar to copper(II) or copper(I) halides as catalyst; the chlorides of Cr(III) and Co(II) are moderately effective, while the chlorides of Mn(II), Fe(III), Fe(II), Zn(II), Ag(I), Cd(II), Hg(II), Hg(I), Tl(III), and Tl(I) are almost ineffective.The use of the pyridine complex of copper or nickel halides suppresses the reaction.The reaction is presumed to proceed via (i) the polarization of the Se-CN bond by coordination of the effective metal salt to the cyano group and (ii) a nucleophilic attack of olefin on the polarized selenium.The substituent parameters of phenylseleno and selenocyanato groups for 13C NMR have been found to be +13 and +15 to 16 ppm for the α carbon and +6 and +6 to 7 ppm for the β carbon, respectively.