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Synthesis And Utility Of Chiral And Achiral Trifluoroacetamide Substrates In Cycloaddition Reactions, Isaac Theodore Smith
Synthesis And Utility Of Chiral And Achiral Trifluoroacetamide Substrates In Cycloaddition Reactions, Isaac Theodore Smith
Theses and Dissertations
In this document we report the synthesis, characterization, and utility of a chiral amidoacrylate substrate. This substrate features a reactive alkene that can be used in a variety of reactions. [3+2]-Cycloaddition reactions to form pyrroloindolines are shown to proceed with excellent diastereoselectivity (>20:1) and yield (86%). [3+2]-Reactions allow for the stereoselective construction of the pyrroloindoline backbone common in many natural products. Diels-Alder reactions catalyzed by TiCl4 show high yields (82%) with ~2:1 diastereoselectivity. Cyclopropanation reactions proceed in moderate yield (71%) and diastereoselectivity (~3:1). Both Diels-Alder and cyclopropanation reactions utilizing the chiral amidoacrylate substrate serve to stereoselectively produce unnatural amino …
Photocycloaddition Of Allenes, Crystal Ward
Photocycloaddition Of Allenes, Crystal Ward
Theses and Dissertations
For the past ten years the Fleming research group has been involved in the research of allene compounds. We have explored the synthesis of allenes as well as several reactions involving allenes, such as oxidation and nitrene addition. Recently, we have explored the synthesis and photochemistry of allenic alcohols tethered to silicon. There are literature examples using allenes in synthesis, but very few examples exist using allenes in photochemical cycloaddition reactions. We have found that a diisopropylallenyloxy(cinnamyloxy)silane derivative undergoes [2+2] photochemical cycloaddition to produce a cyclobutylsilane product when irradiated for 60-75 minutes.