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Full-Text Articles in Physical Sciences and Mathematics
Allylic Benzoate Reductions: A Study On Stereospecificity, Michael A. Leitch
Allylic Benzoate Reductions: A Study On Stereospecificity, Michael A. Leitch
WWU Graduate School Collection
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. …
Development Of Regio- And Diastereoselective Samarium (Ii) Iodide Mediated Allylic Benzoate Reductions, Trevor Stockdale
Development Of Regio- And Diastereoselective Samarium (Ii) Iodide Mediated Allylic Benzoate Reductions, Trevor Stockdale
WWU Graduate School Collection
Herein, we report a regio- and diastereoselective samarium mediated allylic benzoate reduction. The reaction can achieve high yields, regioselectivity, and diastereoselectivity, however there appear to be many factors influencing the outcome: proton sources, alkene geometry, chelating group length, relative stereocenter positioning, and stereocenter identity. These substrate parameters were looked at in-depth which ultimately led to several conclusions about optimized substrates. For instance, experiments indicate that the reaction proceeds through a bicyclic organosamarium species followed by intramolecular protonation from samarium bound water.