The addition of arenesulfenyl chlorides to quadricyclene has been investigated. These reactions are rapid, exothermic and yield primairly three isomers. Two of the isomers (type I and type II structures) have the norbornene and nortricyclene carbon skeletons respectively. The structure of the nortricyclene isomer has been thoroughly established with a wide variety of techniques including 2D NMR. It has been found that a bridged sulfonium ion is not an important product precurser in these electrophilic addition reactions. In a attempt to force the formation of a bridged ion, preliminary studies using arenesulfenyl chlorides in which the aromatic ring contains electron-donating groups have been carried out. The results of these reactions suggest that the amount of bridged ion precurser present is minor at best. Studies of the ratio of isomers I to I I to I 1 1 reveal complex patterns, and suggest conclusions about kinetic control. In summary, a significant niche in mechanistic theory has been established, but more exploration would be necessary to induce bridged ion formation and to completely establish all the caveats of this process.
Library of Congress Subject Headings
Cyclopropane; Isomerization; Chlorides; Stereoisomers
Department, Program, or Center
School of Chemistry and Materials Science (COS)
Niger, Robert J., "Addition of arenesulfenyl chlorides to quadricyclene" (1992). Thesis. Rochester Institute of Technology. Accessed from
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