Date of Award
Program or Major
Master of Science
Charles K Zercher
Arthur H Greenberg
Christopher F Bauer
The investigation of homologation-cyclopropanation in β-diketones revealed the involvement of two donor-acceptor cyclopropane intermediates. Cyclopropanoxide rearrangements were accomplished using reaction conditions other than zinc-carbenoid. Ring fragmentation within chain-extended tertiary cyclopropanoxides was investigated under acidic and basic reaction conditions.
Tandem chain extension-aldol reaction and lactonization were accomplished using α-carboxyester imides. A diastereomeric mixture of substituted γ-lactones (cis and trans) was isolated and characterized by NMR studies. Increased diastereomeric ratios of the trans substituted γ-lactones versus their cis counterparts were attributed towards increased syn-aldol selectivity due to chelation of the zinc-bound ester enolate with the imide carbonyl of the chiral auxiliary.
Bala, Kaushik Badri, "I. Zinc mediated homologation-cyclopropanation in beta diketones and selectivity within cyclopropanoxide rearrangements. II. Zinc mediated tandem chain extension-aldol reaction and formation of substituted gamma lactones" (2016). Master's Theses and Capstones. 1072.