Manabu Ishifune

Cathodic coupling of aliphatic esters. Useful reaction for the synthesis of 1,2-diketone and acyloin

Abstract It has been found in this study that electroreduction of aliphatic ester (1) with Mg electrode leads to the formation of the corresponding 1,2-diketone under aprotic conditions, whereas bis(trimethylsilyloxy)alkene is afforded through acyloin condensation when the reduction is carried out in the presence of chlorotrimethylsilane.

Cathodic intra- and intermolecular couplings of ketones with unsaturated silanes

Abstract The electroreduction of 6-trimethylsilyl-6-hepten-2-one afforded cis -1-methyl-3-trimethylsilyl cyclohexanol, and γ-trimethylsilyl alcohols were yielded as the intermolecular coupling products when the cathodic reduction of ketones was carried out in the presence of unsaturated silanes.

Formation of a reasonably stabilized trichloromethyl anion by the reaction of chloroform with electrogenerated base, and its 1,4-addition to α,β-unsaturated carbonyl compounds

Abstract A reasonably stabilized trichloromethyl anion (TCMA) was formed by the reaction of chloroform with an electrogenerated base prepared by the electroreduction of 2-pyrrolidone, and the addition of this TCMA to α,β-unsaturated esters gave the corresponding β-trichloromethyl esters in good yields.

Electroreductive formation of polysilanes

Electroreduction of dichlorosilanes, such as 1,1-dichlorodialkylsilanes, 1,2-dichlorotetra-alkyldisilanes, and 1,4-bis(chlorodialkylsilyl)benzenes, with Mg electrodes in a single-compartment cell was found to yield the corresponding polysilanes.

Electroreductive coupling of aliphatic amides. A useful method for the synthesis of α-amino ketones☆

Abstract Electroreduction of aliphatic amides (RCONMe2) with Mg electrode in the presence of chlorotrimethylsilane (TMSCI) has been found to give the coupling products [R(TMSO)C C(NMe2)R] and hydrolysis of the products affords the corresponding α-amino ketones [RCOCH(NMe2)R] in excellent yields.

Cathodic coupling of ketones with trimethylsilyl substituted allyl alcohols

Abstract Cathodic coupling of ketones with 3-(trimethylsilyl)allyl alcohols has been found to give trimethylsilyl substituted 1,3-diols with high diastereoselectivity, whereas that with 2-(trimethylsilyl)allyl alcohols afforded homoallylic alcohols through the Peterson elimination of intermediately formed trimethylsilyl substituted 1,4-diols.

A novel electroreductive alkylation of cycloheptatriene systems and its application to facile synthesis of β-thujaplicin☆

Abstract Electroreduction of cycloheptatriene or substituted cycloheptatrienes in the presence of an alkyl halide was found to be a unique and effective method for introducing regioselectively an alkyl group into seven-membered ring system and it was applied to a new synthesis of β-thujaplicin (hinokitiol).