Practical and Powerful Synthetic Organic Methods Using Silanes

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Synthetic organic chemistry enables access to important and useful molecules that affect all aspects of life. These molecules may be previously known (e.g. a scarcely available biologically active natural product) or unknown (e.g. a bespoke monomer for an interesting new material), but in either case the chemist must have a sufficient toolkit with which to work to be able to generate the molecule of interest for further application or study. Chemical reactions involving organic molecules require the use of reagents and/or catalysts to enable these transformations. Currently the most powerful of these synthetic tools contain transition metals; while efficient, such methods have significant drawbacks such as cost, practicality, toxicity, and/or significant environmental impact. Organosilanes - organic molecules containing silicon - lack many of the undesirable attributes of transition-metal-containing organometallic compounds: silicon is naturally abundant and thus inexpensive, generally non-toxic and easy to work with, and readily available in a variety of functional forms. Yet their use for organic synthesis is limited due to a lack of development of functional and practical reagents and/or catalysts. The current selection of synthetically useful organosilanes are limited in utility. For atom-transfer reactions, milder reagents such as trialkylsilanes require forceful activation, and more reactive ones such as trialkoxy- or trihalosilanes are difficult and/or hazardous to handle. Beyond a very few highly reactive Lewis acids, there are no existing silicon-based catalysts. This proposal seeks to develop novel silanes as cutting edge tools for organic synthesis. We propose that the key to unlocking the potential of organosilanes as highly functional indispensable tools in organic synthesis is to harness the power of stable and meta-stable hypercoordinate silanes, and we will explore this idea through the projects detailed in the proposal. The synthetic tools being developed will be of high value, allowing more ready access to important molecules that impact not only chemical studies but also adjoining fields such as biochemistry, biology, and materials. Furthermore, this work will expand on not just a singular technology, but significantly mature a vital subfield within synthetic chemistry, namely the use of silanes as powerful, accessible, cheaply available, easy-to-handle, and readily controlled organic reagents and catalysts. This general idea will continue to be explored in our lab to reveal new modes of reactivity and inspire others to pursue these underutilized molecules.