<p> The first part of this thesis is a story about the design and optimization of synthetic methodology for the preparation of complex secondary and tertiary phosphine oxides. A scalable, single-step, acid-catalyzed addition-rearrangement cascade that couples aldehydes with primary phosphines to give racemic unsymmetrical secondary phosphine oxides (SPOs) was developed based on the observations and hypotheses reported in a collection of papers published in the early 1960s. Most of this work was reported in a communication published in Organometallics (<i>Organometallics</i>, <b>2010</b>, <i>29</i>, 4193-4195).</p><p> A general method for kinetic resolution of racemic SPOs by asymmetric catalytic arylation was the next target, but this required a catalyst and conditions that would operate at room temperature. After finding that a Xantphos-Pd complex suited this purpose, and demonstrating broad utility and stereospecific coupling, an optically active analog of Xantphos was designed and synthesized. When combined with palladium, this "Slantphos" catalyzed the arylation of racemic SPOs, with modest stereoenrichment. Much of this work was reported in a communication published in Organic Letters (<i>Org. Lett.</i>, <b> 2012</b>, <i>14</i>, 4370-4373).</p><p> The second part of this dissertation details the discovery of a novel class of materials, some of which are highly active catalysts for the electrochemical oxidation of water. The most active of these catalysts was selected for detailed electrochemical studies in several different electrolytes. At pH 7, borate was found to be superior. Several studies were also undertaken to characterize the material before and after catalysis, but the structure remains undetermined. Most of this work was reported in a full paper published in the New Journal of Chemistry (published online January 15, 2014).</p>
| Identifer | oai:union.ndltd.org:PROQUEST/oai:pqdtoai.proquest.com:3580637 |
| Date | 26 June 2014 |
| Creators | Bloomfield, Aaron James |
| Publisher | Yale University |
| Source Sets | ProQuest.com |
| Language | English |
| Detected Language | English |
| Type | thesis |
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