Competitive binding of fluorosulfate anion in reactions of halogens and nitronium borofluoride with olefins

Conclusions Reactions of olefins with chlorine in the presence of fluorosulfonic acid salts lead to-chloroalkyl fluorosulfates together with 1,2-dichlorides. The addition of nitronium borofluoride to ethylene in the presence of tetraethylammonium fluorosulfate gives 2-nitroethyl fluorosulfate. These reactions confirm the general character of the competitive binding of superweak nucleophiles in Ad_E reactions.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 2, pp. 389–391, February, 1985.     

Novel method of deoxidation of alcohols and its use in synthesis of covalent perchlorates

Alcohols can be effectively deoxidated by treatment with chlorine and sulfur in the presence of pyridine with incorporation of an external nucleophile from added salts.     

Amino acid-derived iodobenzene dicarboxylates: reagents for oxidative conversion of alkenes to amino acid esters

[reaction: see text] New amino acid-derived iodobenzene dicarboxylates were prepared by the reaction of (diacetoxyiodo)benzene with N-protected natural amino acids. These compounds in the presence of iodide anion can be used as reagents for beta-iodocarboxylation of alkenes leading to the respective amino acid esters.     

Preparation,structure, and unexpected chemistry of phosphoranyl-derived benziodoxoles

Novel phosphoranyl-derived benziodoxoles were prepared by the reaction of 1-acetoxybenziodoxole with stabilized phosphonium ylides [1-triphenylphosphoranylidene-2-propanone and (carbomethoxymethyl)triphenylphosphoranylidene acetate]. X-ray crystallographic analysis of these compounds demonstrates the significance of secondary bonding interactions, which link individual molecules into infinite chains. An unusual ligand exchange on an iodine(III) center resulting in the substitution of a carbon ligand with an oxygen ligand was observed in the reaction of these compounds with strong acids.     

Preparation of bis(heteroaryl)iodonium salts via an iodonium transfer reaction between di(cyano)iodonium triflate and organostannes

Di(cyano)iodonium triflate 5 generated in situ from iodosyl triflate (0 = I-OTf) and cyanotrimethylsilane is a preferred reagent for the preparation of various bis(heteroaryl)iodonium triflate salts 11–15 via an iodonium transfer reaction with the corresponding tributyltin substituted heterocycles 6–10 . Novel heteroaromatic iodonium salts 3, 11–15 were isolated in good yields as relatively stable microcrystalline solids and characterized by multinuclear nmr, ir and hrms data.     

Fluoroxenonium derivatives as reagents for the functionalization of olefins to giveβ-fluoroalkyl triflates, β-fluoroalkyl fluorosulfates,andβ-fluoroalkyl nitrates

Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1196–1197.