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Date of Award
Department or Program Affiliation
Master of Science (MS)
O'Neil, Gregory (Gregory W.)
Vyvyan, James R.
Gilbertson, John D.
Herein we report results from experiments aimed at better understanding SmI2(H2O)n reductions of allylic benzoates adjacent to a trisubstituted alkene. When flanked by both a chelating group and stereodirecting group, these reactions can occur with complete regioselectivity and good diastereoselectivity (up to 90:10). Initial experiments suggested that the reaction was stereospecific to alkene geometry. However, further experimentation has revealed that the alkene stereospecificity is substrate dependent. For instance, if the geminal alkene substituents are alkyl, results show the reaction to be stereospecific, but if one of the substituents is a phenyl group the reaction is still stereoselective but not stereospecific. This was demonstrated through the synthesis and subsequent SmI2(H2O)n reduction of a series of cis- and trans-allylic benzoate isomers followed by careful analysis of the product mixtures by 1H NMR. To explain these results our current working hypothesis is based on formation of an η3-organosamarium bicyclic intermediate. In some cases, C-C bond rotation in the pi-allyl intermediate relieves steric strain, leading to a loss in stereospecificity.
allyl, organosamarium, stereospecific, stereoselective
Western Washington University
Subject – LCSH
Samarium; Acrolein; Benzoates; Reduction (Chemistry)
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Leitch, Michael A., "Allylic Benzoate Reductions: A Study on Stereospecificity" (2020). WWU Graduate School Collection. 959.