Oxyselenenylation deselenenylation

The electrochemical oxyselenenylation-deselenenylation of alkenes was demonstrated by a one-step 92% synthesis of ( )-dihydroactinidiolide (187) from the carboxylic acid (186) (81JA4606). 

The first example of a catalytic approach to the selenium promoted conversion was reported by Torii, who described an oxyselenenylation-deselenenylation process using catalytic amounts of diphenyl diselenide [115]. The electrophilic species was produced from the diselenide by electrochemical oxidation in the presence of the alkene 233 in methanol or in water. As indicated in Scheme 36, the addition product is electrochemically oxidized to afford the selenoxide which by elimination gives the allylic ether or alcohol 234 and the phenylselene-nic acid which continues the cycle by adding again to the alkene 233. 

Scheme 36. Electrochemical Catalytic Oxyselenenylation-Deselenenylation of Alkenes...

As an electrochemical reaction, Torii and co-workers demonstrated that the facile transformation of alkenes into allylic alcohols and ethers proceeded in the presence of a catalytic amount (10 mol%) of diphenyl diselenide (Scheme 15) [18]. Most of terminal co double bonds of isoprenoids undergo regioselective oxyselenenylation-deselenenylation to give frans-allylic alcohols in aqueous acetonitrile and methyl ethers in methanol. The addition of SOI salts improves chemical yields since SOI salts prevent the conversion of phenylselenenic acid (PhSeOH) into the inert phenylseleninic acid (PhSe02H) by both disproportionation and electro-oxidation. This method was also applied to intramolecular reaction to form -lactone in high yield. 

Oxyselenenylation-oxidative deselenenylation (oxyselenenylation-selenoxide elimination) sequence provides the double-bond transpositioned allylic alcohols and ethers from alkenes. Oxyselenenylation of alkenes and its asymmetric... 

The first catalytic asymmetric oxyselenenylation-oxidative deselenenylation reaction was reported by Tomoda and co-workers in 1994 [26]. The treatment of... 

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