Vladimir O. Smirnov

Synthesis of gem-difluorinated nitroso compounds.

A method for the synthesis of gem-difluorinated nitroso compounds is described. The reaction involves interaction of organozinc reagents with (bromodifluoromethyl)trimethylsilane followed by nitrosation of difluorinated organozinc species with an n-butyl nitrite/chlorotrimethylsilane system.

Synthesis of 3-Fluoroindoles via Photoredox Catalysis

A method for the synthesis of 3-fluoroindoles from N-arylamines substituted with the CF2I group is described. The reaction is mediated by a ruthenium photocatalyst in the presence of a substoichiometric amount of triphenylphosphine upon irradiation with blue light. The starting N-arylamines are readily obtained by nucleophilic iododifluoromethylation of iminium ions.

Nucleophilic Iododifluoromethylation of Aldehydes Using Bromine/Iodine Exchange

A method for the iododifluoromethylation of aromatic aldehydes using (bromodifluoromethyl)trimethylsilane (Me3SiCF2Br) is described. The selective formation of the CF2I group is based on using sodium iodide, with the sodium serving as a scavenger of bromide and iodide serving as a nucleophile with respect to difluorocarbene. The primary CF2I-addition products can undergo HI-elimination or iodine/zinc exchange followed by allylation in a one-pot manner.

Reactions of 1,1-difluoroalkylzinc halides with chlorinating reagents

Compounds bearing chlorodifluoromethyl group can be assembled from organozinc chlorides, (chlorodifluoromethyl)trimethylsilane (Me3SiCF2Cl), and sulfuryl chloride as a chlorine source. Reactions of 1,1-difluoro-substituted organozinc bromides (RCF2ZnBr) with different chlorinating reagents lead to predominant or partial formation of the products bearing bromodifluoromethyl group.

Silylation of γ, γ-bis(alkoxycarbonyl)-substituted aliphatic nitro compounds: Synthesis of N, N-bis(trimethylsilyloxy)aminocyclopropanes

Silylation of γ,γ-bis(alkyloxycarbonyl)-β-aryl- and γ,γ-bis(alkyloxycarbonyl)-β-alkyl-substituted aliphatic nitro compounds proceeds stereoselectively to give the corresponding N,N-bis(trimethylsilyloxy)aminocyclopropanes in high yields. These compounds can be used as synthetic equivalents of nitrosocyclopropanes.

General Synthesis of γ-Functionalized β-Aryl-Substituted Primary Nitro Compound

A simple and general procedure was developed for synthesis of γ-functionalized β-aryl-substituted; primary nitro compounds from aromatic aldehydes, carbonyl compounds with an activated methylene group, and nitromethane.