M. I. Lazareva

Direct remote oxidation of aliphatic ketones to δ- andδ-diketones

Abstract Aliphatic ketones are converted into °- and °-diketones in one-pot oxidation reaction on treatment with Na2S2O8 in presence of Fe(II)ions.

Regioselective one-step γ-chlorination of alkanesulfonamides. Preponderance of 1,5-H migration from sulfonyl versus amide moiety in sulfonylamidyl radicals

Alkanesulfomides 1 are converted regioselectively into 3-chloroalkane-sulfonamides 2 in one-pot reaction with Na2S2O8-CuCl2. N-Amylbutanesulfonamide 7 is substituted predominantly on sulfonyl moiety.

Regiospecific oxidative cyclization of N-methanesulfonylalkylamines: a new method of pyrrolidine ring construction

Abstract N-Methanesulfonylalkylamines cyclize regiospecifically into N-methanesulfonylpyrrolidines in one-pot oxidation reaction in Na 2S2O8-CuCl2.

New potentialities of electrophilic addition in the assembly of polyfunctional compounds from simple precursors

A novel methodology of the multicomponent coupling based on the controlled sequence of the kinetically independent electrophilic additions is suggested and its promise as an efficient protocol for the short synthesis of the structurally diverse polyfunctional compounds from simple precursors is demonstrated.

Four-component couplingvia a sequence of threeAd E reactions involving arenesulfenyl chloride, two alkyl vinyl ether units, and silicon-containing π-donors as a method for the synthesis of polyfunctional compounds

A protocol for the synthesis of polyfunctional compounds by a Lewis acid initiated tandem sequence of threeAdE reactions of sulfur-containing electrophiles with two alkyl vinyl ether units and silicon containing π-donors is proposed.

Diastereoselective synthesis of polyfunctional compounds based on the tandem sequence of threeAd E reactions using cyclic vinyl ethers as first alkene components

The reaction of the bicyclic thiophanium ions salts, generated by the sequential interaction ofp-TolSCI with dihydropyran or 1-methoxycycloalkene and then with an acyclic alkyl vinyl ether in the presence of a Lewis acid and with silicon- or tin-capped π-donors, proceeds with high diastereoselectivity at all newly created chiral centers.

Remote oxidation of ketones to γ- and δ-diketones

A single stage remote oxidation of ketones to γ- and δ-diketones has been carried out in a sodium peroxysulfate-iron(II) sulfate system.

Polyfunctional adducts assembled with the help of a one-pot sequence of three AdE reactions as synthetically useful intermediates. The course of the Lewis acid induced transformations of the 4,6-dialkoxy-7-arylthioheptene moiety

Abstract Data on the selectivity of the Lewis acid induced transformations of the title adducts are presented and the routes leading to formation of products containing either cyclohexane or 1,3-dienes units are described.

Reactions of nitronates derived from simple nitro alkanes with some thio-stabilized cationic intermediates

Trimethylsilyl and DBU nitronates derived from nitromethane and nitropropanes do not undergoC-alkylation by episulfonium (ESI) or thiophanium (TPI) cationic intermediates. The above-mentioned derivatives of 1-nitropropane react with ESI and TPI to give the corresponding products ofO-alkylation of 1-chloro-1-oxyiminopropane. The reactions of DBU nitronates derived from nitromethane and 2-nitropropane with ESI or TPI proceed asO-alkylation followed by standard fragmentation of the initially formed nitronate intermediates to give methyl (4-tolylthio)acetate or methyl 2,2-dimethyl-3-methyloxy-(4-tolylthio)butanoate respectively.

Polar control in the remote oxidative functionalization of sulfones

Conclusions1.Oxidation of dialkyl sulfones with systems containing sodium peroxydisulfate results in remote functionalization, the site of which is dependent on the length of the alkyl chain, in agreement with polar control of this reaction by the electron-acceptor sulfonyl group.2.Butyl alkyl sulfones are selectively oxidized by Na2S2O8 to 3-oxobutyl alkyl sulfones, and oxidative chlorination in the system Na2S2O8-CuCl2 gives 3- and 4-chlorobutyl alkyl sulfones, the γ-chlorination products predominating.