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 acids which can serve as building blocks for natural products or aid in peptide stabilization. Further chiral Lewis acid catalyzed studies using an achiral amidoacrylate substrate are also explored.
College and Department
Physical and Mathematical Sciences; Chemistry and Biochemistry
BYU ScholarsArchive Citation
Smith, Isaac Theodore, "Synthesis and Utility of Chiral and Achiral Trifluoroacetamide Substrates in Cycloaddition Reactions" (2021). Theses and Dissertations. 9683.
Acetamide, amidoacrylate, Diels-Alder, Cyclopropanation, Cycloaddition, Evans auxiliary