Title:

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

Author(s):

Allen, Julia Margaret

Thesis Advisor(s):

Lambert, Tristan H.

Date:

2011

Type:

Dissertations

Department:

Chemistry

Permanent URL:

http://hdl.handle.net/10022/AC:P:10595

Notes:

Ph.D., Columbia University.

Abstract:

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.

Subject(s):

Organic chemistry

Item views:

179

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