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Published data on the structure, properties and methods for the synthesis of inorganic sulfonates of polyvalent iodine are surveyed. Primary attention is devoted to the reactions of these compounds with organic substrates. The bibliography includes 129 references.

Various approaches used for analyzing and predicting reactivity in nucleophilic substitution reactions at saturated carbon atoms were systematized and compared. The similarities between these approaches, their scopes, advantages, and disadvantages were established. The trends and outlooks in the further development of qualitative and quantitative models for describing dependences of the reactivities of substances on the physicochemical properties of substrates and nucleophiles were analyzed.

UV irradiation-initiated addition of CF 2 Br 2 ( 2 ) and BrCF 2 CF 2 Br ( 3 ) to propellane ( 1 ) has been found to occur giving 1,3-disubstituted bicyclo[1.1.1]pentanes ( 4 ) and ( 6 ), and ‘staffanes’ ( 5 ) and ( 7 ). In the case of reaction with BrCF 2 CF 2 Br, the product ( 8 ) was also isolated. The relative stability of fluorinated radicals and their influence on product formation are discussed.

Allene 1 reacts with PhIO/BF 3 .Et 2 O or PhIF 2 /BF 3 .Et 2 O in CH 2 Cl 2 at -60 o C with the formation of novel phenyldihydrofuryliodonium salts 2. Molecular structures for both products 2a,b are determined by X-ray analysis. Iodonium perchlorate 2b reacts with the anionic nucleophiles (NaN 3 , NaOCH 3 , NaOC 2 H 5 , CuI/KI) to give the corresponding products of the vinylic nucleophilic substitution (6a-e) of the iodobenzene moiety

Iodosyl fluorosulfate (1) reacts with aromatic compounds (2) under mild conditions to give diaryliodonium hydrosulfates (3) in good yield

Published data on the structure, properties and methods for the synthesis of inorganic sulfonates of polyvalent iodine are surveyed. Primary attention is devoted to the reactions of these compounds with organic substrates. The bibliography includes 129 references.

Allene 1 reacts with PhIO/BF 3 .Et 2 O or PhIF 2 /BF 3 .Et 2 O in CH 2 Cl 2 at -60 o C with the formation of novel phenyldihydrofuryliodonium salts 2. Molecular structures for both products 2a,b are determined by X-ray analysis. Iodonium perchlorate 2b reacts with the anionic nucleophiles (NaN 3 , NaOCH 3 , NaOC 2 H 5 , CuI/KI) to give the corresponding products of the vinylic nucleophilic substitution (6a-e) of the iodobenzene moiety

UV irradiation-initiated addition of CF 2 Br 2 ( 2 ) and BrCF 2 CF 2 Br ( 3 ) to propellane ( 1 ) has been found to occur giving 1,3-disubstituted bicyclo[1.1.1]pentanes ( 4 ) and ( 6 ), and ‘staffanes’ ( 5 ) and ( 7 ). In the case of reaction with BrCF 2 CF 2 Br, the product ( 8 ) was also isolated. The relative stability of fluorinated radicals and their influence on product formation are discussed.

Iodosyl fluorosulfate (1) reacts with aromatic compounds (2) under mild conditions to give diaryliodonium hydrosulfates (3) in good yield

Reaction of XeF 2 with SO 3 proceeds to give either FXeOSO 2 F ( 3 ) or Xe(OSO 2 F) 2 ( 4 ) depending on the reagent ratio. Both these reagents react with weakly nucleophilic halogenated olefins to give halogenoalkylfluorosulfates 6 and 7 .

Reaction of difluoronitro- and fluorochloronitroacetic acids with aromatic substrates in the presence of XeF 2 results in alkylation of the aromatic ring by the O 2 NF 2 C· and O 2 NFCIC· radicals.

A three-dimensional diagram obtained from the More O'Ferrall plot by the addition of one more perpendicular coordinate reflecting the biradicaloid character of the transition state is proposed for analysis of S N reactions.

The molecular structure of the trans addition product of Hg(OAc)2 to diester 1 has been determined by X-ray diffraction (represented by formula 3 ) which leads to a revision of previously claimed cis -additions in this series.

The addition of cesium fluoroxysulfate (1) to a variety of alkenes (1-hexene, styrene, E-stilbene, cyclohexene, diene 14) proceeds under mild conditions giving the previously unknown vicinal fluoro alkyl sulfates. The structures of these products were rigorously established by thorough 1 H, 19 F and 13 C NMR data analyses. The studied reactions exhibit low regio- and stereo- selectivities with a preference for anti-Markovnikov- and syn-addition. The predominance of cis-product formation is consistent with a concerted mechanism for the addition.

Heterocyclization of 5,6-disubstituted 2-allylthio(oxy)-4-oxothieno[2,3-d]pyrimidines by treatment with halogens affords thieno[3,2-e]thiazolo[3,2-a]pyrimidine iminium salts. Treatment of these salts with aqueous sodium acetate results in cleavage of the thiazoline ring.

Iodosobenzene tetrafluoroborate 1 ha been prepared by the reaction of PhI(OAc) 2 and aquenous HBF 4 , and its reactions with alkenes, silyl enol ethers, and acetylenes have been studied.

“doping-addition” of 2-NO 2 C 6 H 4 SCl to the tricyclo[4,2,2,0 2,5 ]deca-3,7,9-triene system occurs to give unusual products: (i) rearranged caged cyclopropane and (ii) the stable cross-perchlorate .

1,4-Dihalo-substituted tellurolanes were obtained by reaction of tellurium tetrabromide and tetrachloride with 1,5-hexadiene, and the corresponding six-membered heterocyclic compounds with a tellurium atom in the ring were obtained with 1,6-diolefins.

New reactions, halogenoperchloration and arylsulfenylperchloration of olefins of the tricyclo[4,2,2,02,5]decane series are described. Stable covalent perchlorates have been isolated in pure form in these reactions. Some important mechanistic and stereochemical features of these processes are discussed.

La reaction d'iodures d'alkyle avec le chlore ou le tetrafluoroborate de nitryle en presence de perchlorates ou d'alcanesulfonates d'ammonium donne des perchlorates d'alkyle et des alcanesulfonates d'alkyle

The “doping-addition” of RSCl to the tricyclo[4,2,2,02,5]deca-3,7-diene derivatives which are incapable of lactone ring closure proceeds to give the novel type of rearranged product, 7 , due to the two subsequent 1,2-shifts.

Heterocyclic compounds containing a selenium (IV) atom as the heteroatom were obtained by the action of selenium tetrahalides on 1,5 and 1,6-diolefins and their derivatives.

Proton-decoupled carbon-13 magnetic resonance spectra of a series of cyclopropane derivatives have been studied. For stereoisomeric substituted 2-phenylcyclopropanes a difference between the isomers has been found in the shieldings of the three-membered cyclic carbons as well as in the shieldings of the carbons of the substituents. The chemical shifts have been interpreted on the basis of an additive approach worked out in a study of the spectra of monosubstituted cyclopropanes and substituted 2,2-diphenylcyclopropanes. Some simple rules have been proposed, which are useful in distinguishing stereoisomeric 1,2-disubstiuted cyclopropanes.

Reactions of olefins with chlorine in the presence of fluorosulfonic acid salts lead toβ-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 AdE reactions.

2,3-Disubstituted 2,3-dihydrobenzo[b]selenophenes were obtained in the form of trans isomers by the action of selenium tetrabromide on dibenzal- and benzalacetone in benzene.

The corresponding halo derivatives of 2-selenaadamantane were obtained by reaction of bicyclonona-3,7-diene with selenium tetrahalides. The structures of the reaction products were confirmed by the results of analysis and PMR and IR spectral data.

The addition of cesium fluoroxysulfate (1) to a variety of alkenes (1-hexene, styrene, E-stilbene, cyclohexene, diene 14) proceeds under mild conditions giving the previously unknown vicinal fluoro alkyl sulfates. The structures of these products were rigorously established by thorough 1 H, 19 F and 13 C NMR data analyses. The studied reactions exhibit low regio- and stereo- selectivities with a preference for anti-Markovnikov- and syn-addition. The predominance of cis-product formation is consistent with a concerted mechanism for the addition.

A series of novel I(III) containing reagents have been developed and their electrophilic reactions with olefins giving vic -disubstituted derivatives (including vic -ditriflates) are described.

A simple method for method for new carbon-carbon bond formation in AdE reactions using the PhIO·HBF4 complex and silyl enol ethers has been developed.