Date of Award
2014
Document Type
Dissertation
Publication Status
Version of Record
Submission Date
October 2026
Thesis/Dissertation Advisor [Chair]
Lepore, Salvatore D.
Abstract
We report here the development of a Lewis acid catalyzed method for the dehydrative coupling of cyclic alcohols and nitriles to form amides with retention of configuration. By contrast, the formation of amides by nitrile trapping of carbocations (Ritter reaction) usually affords racemic product. The present reaction was accomplished by first converting alcohol starting materials to their corresponding chlorosulfites in situ. Even after an extensive search, only copper (II) salts were able to produce the desired conversion of these chlorosulfites to amides though with low catalytic turnover. Improving the turnover without deteriorating the stereochemical outcome was eventually accomplished by a careful selection of the reagent addition sequence and through the removal of gaseous byproducts. This Ritter-like coupling reaction proceeds in good yields with secondary cyclic alcohols under mild conditions. The stereochemical outcome likely due to fast nucleophilic capture of a non-planar carbocations (hyperconjomers) stabilized by ring hyperconjugation.
Extent
153 p.
Recommended Citation
Alhuniti, Mohammed, "New stereoselective reactions to form amido alkyl c-n and vinyl triflate c-o bonds via carbocation intermediates & ultrafast silicon fluorination methodologies for applications in pet imaging" (2014). Electronic Theses and Dissertations 2010 - 2019. 1065.
https://digitalcommons.fau.edu/etd_general_6/1065
Identifier
FA00004262
Comments
Includes bibliography.|Dissertation (Ph.D.)--Florida Atlantic University, 2014.|FAU Electronic Theses and Dissertations Collection|Includes bibliography.