chemistry major, basic organic chemistry skills in theory and practice
as the non-methylated parent compound?In synthetic organic chemistry, most of the already existing photoreactive compounds are used as protecting groups that can be cleaved with UV light to liberate alcohols, carboxylic acids, and amines. Unlike ordinary photoreactive protecting groups, N-acyl-nitroindolines are a special group of photoreactive compounds that are capable of an acyl transfer to a variety of nucleophiles, such as amines, aminals, hydrazine, alcohols, and thiols (see for example two publications from our research group: Kaneshiro & Michael, Angew. Chem. Int. Ed. 2006, 45, 1077; and Pardo et al., ChemBioChem 2015, 16, 1884). These photochemical acylation reactions produce amides, oxoesters, thioesters, and hydrazides under mild conditions, and are therefore very useful synthetic tool. There are a number of nucleophiles that have never been explored in this acyl transfer photochemistry, e.g. organometallic reagents, enolates, and azides. Based on the published photolysis mechanism of N-acyl-nitroindolines (Morrison et al., Photochem. Photobiol. Sci. 2002, 1, 960) we expect that the illumination of N-acylnitroindolines in the presence of these nucleophiles can produce aldehydes, ketones, acylazides, and dicarbonyl compounds.
The undergraduate student will receive training in the laboratory techniques required for the synthesis of small organic molecules, in synthetic photochemistry, in compound purification by chromatography, and in compound analysis by mass spectrometry, infrared spectroscopy, and 1H and 13C nuclear magnetic resonance spectroscopy.