New Anionic Annulation Reactions and Anion Accelerated Amino-Cope Rearrangement
AdvisorNjardarson, Jon T.
MetadataShow full item record
PublisherThe University of Arizona.
RightsCopyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author.
EmbargoRelease after 01-Jul-2017
AbstractNew Anionic Annulation Reactions and Anion Accelerated Amino-Cope Rearrangement. This dissertation compiles asymmetric anionic reactions of chiral Ellman sulfinyl imines and dienolates to access diverse nitrogen-containing compounds. Chiral sulfinimines and dienolates derived from 𝛾-bromocrotonates reacted diastereoselectively forming 3-pyrrolines and 𝑐𝑖𝑠-vinyl aziridines via a formal [3+2]-annulation and vinylogous 𝑎𝑧𝑎-Darzens reactions respectively. Concise asymmetric syntheses of three natural products have been achieved demonstrating the power of the [3+2]-methodology. Reaction of conjugated sulfinimines with enolates derived from non-halogen containing crotonates, were found to undergo a tandem diastereoselective α,α-addition, and anionic [3,3]-rearrangement affording vinylogous amide products. Synthesis of aromatic imines via 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) initiated oxidative aromatization highlights the synthetic value of the accelerated anion amino-Cope rearrangement.
Degree ProgramGraduate College