The silver ion-induced rearrangement of N-chlorocyclobutylamines

Author

Lonnie Bryant

Date of Award

8-1987

Degree Type

Dissertation

Degree Name

Doctor of Philosophy

Major

Chemistry

Major Professor

Fred M. Schell

Committee Members

Ronald M. Magid, James Q. Chambers, Paul Phillips

Abstract

The effect of treating N-chlorocyciobutylamlnes with silver tetrafiuoroborate and a subsequent hydride reduction results in moderate yields of substituted pyrroiidines. Ring-expansion in these reactions presumably results in imminium ions which were found not to react with internal carbon-carbon double bond nucleophiles when re arranged in aprotic media. Similar rearrangements of multiply substituted N-chlorocyclobutylamines produced, after reduction, substituted pyrroiidines whose substitution patterns reflected migration of carbon bonds to the electron-deficient nitrogen center. The formation of these products has consistently been shown to be the result of favorable orbital overlap of the empty orbital on nitrogen and a carbon-carbon bond of the cyciobutyl ring. Which bond of this moiety migrates has been suggested to be dependent on which bond can achieve the least sterically crowded transition state in a trans-anti spatial arrangement with the nitrogen-chlorine orbital bonding.

Recommended Citation

Bryant, Lonnie, "The silver ion-induced rearrangement of N-chlorocyclobutylamines. " PhD diss., University of Tennessee, 1987.
https://trace.tennessee.edu/utk_graddiss/12025