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Novel Reactions Of Donor-Acceptor Cyclopropanes, And Diels-Alder Approach Towards Fargesine And Fumimycin, Polydoros Kyriacou
Novel Reactions Of Donor-Acceptor Cyclopropanes, And Diels-Alder Approach Towards Fargesine And Fumimycin, Polydoros Kyriacou
Electronic Thesis and Dissertation Repository
The first chapter of this thesis consists of two related projects that explore novel reactivity of donor-acceptor cyclopropanes, specifically 2-substituted cyclopropane 1,1-diesters. The first project involves the nucleophilic ring opening of donor-acceptor cyclopropanes with potassium organotrifluoroborates. It was found that during the ring opening of the cyclopropane, the diesters of the cyclopropane formed a malonyl-BF2 complex. The complex could then be hydrolyzed to afford substituted malonates. The reaction was limited to aryl cyclopropanes and potassium alkynyltrifluoroborates. The second project in this chapter explores modifying the Kerr group’s previous synthesis of tetrahydro-1,2-oxazines, such that geminal allyl, methyl esters are now …
The Multicomponent Synthesis Of Pyrroles From Cylcopropane S Using A One Pot Pd(0) Catalyzed Dehydrocarbonylation Protocol, William J. Humenny
The Multicomponent Synthesis Of Pyrroles From Cylcopropane S Using A One Pot Pd(0) Catalyzed Dehydrocarbonylation Protocol, William J. Humenny
Electronic Thesis and Dissertation Repository
Previous work done by the Kerr group has shown that tetrahydro-1,2-oxazines can be efficiently synthesized using a three component coupling reaction between a hydroxylamine, aldehyde and cyclopropane diester. This affords the desired heterocycle efficiently with a wide variety of substitution. When one esters bears an allyl group a Tsuji dehydrocarbonylation reaction may take place resulting in the formation of a 4,5-dihydro-1,2-oxazine. This motif contains a vinylogously acidic proton which is extremely labile and easily deprotonated. Under basic conditions this proton is removed and consequently the N-O bond is cleaved and subsequent condensation occurs forming a pyrrole. Using a sequence of …