Efforts at Expanding the Scope of Peptides as Enantioselective Organic Catalysts

The development of peptides as catalysts for preparing optically active molecules is an ongoing investigation. Efforts at expanding the use of peptides are explored in two ways: investigating novel reactions in which peptides can act as asymmetric catalysts and through expanding the substrate scope of peptides in performing kinetic resolutions. Attempts at furthering the reaction scope of acylsulfonamide-containing peptides to act as BrØnsted acids through promoting the attack of 7-methyl oct-6-ene-1-tosylaziridine (9) by an internal π-nucleophile are discussed herein. Also reported is the use of pentameric peptides containing a π(-methyl)histidine residue in the kinetic resolution of the primary alcohol 4-hydroxymethyl cyclopent-2-enone (76) and the secondary aliphatic alcohol 2- pentanol. Moderate selectivities were observed in the kinetic resolution of 4-hydroxymethyl cyclopent-2-enone (76) and promising results were obtained in the initial screening of catalysts for the resolution of 2-pentanol.Thesis (MS) — Boston College, 2008.Submitted to: Boston College. Graduate School of Arts and Sciences.Discipline: Chemistry