2011 Theses Doctoral
Part 1. Diaziridinium Ions: First Reported Synthesis and Reactivity Studies. Part 2. Tropylium Ion Mediated alpha-Cyanation of Amines. Part 3. Multicatalytic Synthesis of Complex Tetrahydrofurans
The first synthesis and full characterization of a new functionality, called the diaziridinium ion, is reported. The original synthetic intent behind its design was to explore its potential use as a non-metal based N-transfer reagent. During this study, we have uncovered a practical rearrangement to access 2,3-benzodiazepines reliably and efficiently.
Efforts to achieve N-transfer from these species are described and are ongoing. We have identified the tropylium ion as a highly efficient organic-based amine oxidant and have demonstrated its practical use in a one-pot protocol for alpha-aminonitrile synthesis. We also report an application of this new oxidant towards an aza-Cope rearrangement.
Finally, we report a multicatalytic method that uses bismuth(III) triflate to catalyze a nucleophilic addition to an aldehyde followed by hydroalkoxylation to generate highly functionalized tetrahydrofuran rings, a motif that is often encountered in natural product architectures.
- Allen_columbia_0054D_10275.pdf application/pdf 42.4 MB Download File
More About This Work
- Academic Units
- Thesis Advisors
- Lambert, Tristan H.
- Ph.D., Columbia University
- Published Here
- June 27, 2011