I. V. Bodrikov

New method for increasing of electrophilicity of weak electrophiles in addition reactions : Wagner-Meerwein rearrangement in a reaction of 2,4-dinitrobenzenesulfenyl chloride with norbornene

Abstract A new method for increasing of the effective electrophilicity of weak electrophyles in addition reactions has been developed, using as a model reaction the addition of 2,4-dinitrobenzenesulfenyl chloride to norbornene. The features of this reaction and some general problems of an electrophilic addition are discussed.

New method for increasing of effective electrophilicity of weak electrophiles in addition reactions. Rearrangements and cis-addition in reactions of sulphenyl chlorides with norbornene and dimethoxybenzonorbornadiene

Abstract The addition of RSC1 to norbomene and dimethoxybenzonorbornadiene can proceed with Wagner-Meerwein rearrangement. These addition reactions can also undergo a “doping-effect” which increases the effective electrophilicity of sulfenyl chlorides. Addition of ArSCI to dimethoxybenzonorbornadiene can proceed partially with formation of cis-adduct (13a) and of inverted trans-adduct (12b). Evidence for the ion-pair mechanism and important mechanistic and stereochemical consequences are discussed.

New method for increasing of electrophilicity of weak electrophiles in addition reactions: Reactions of 2,4-dinitrobenzenesulphenyl chloride with norbornene and dimethoxybenzonorbornadiene in formic acid

Abstract The effective electrophilicity of 2,4-dinitrobenzenesulphenyl chloride in its addition to norbornene and dimethoxybenzonorbornadiene in formic acid has been studied.

Novel skeletal rearrangement in addition reaction to tricyclo[4,2,2,02,5]deca-3,7-diene system

Abstract 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.

Doping-addition of arylsulfenyl chlorides to the tricyclo[4,2,2,02,5]deca-3,7,9-triene system: skeletal rearrangements and serendipitious products

Abstract “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 .