Practical and Powerful Synthetic Organic Methods Using Silanes

合成有机化学使我们能够接触到影响生活各个方面的重要和有用的分子。这些分子可能是以前已知的（例如，很少有生物活性的天然产物）或未知的（例如，一种有趣的新材料的定制单体），但在任何一种情况下，化学家都必须有足够的工具包来工作，以便能够产生感兴趣的分子以进行进一步的应用或研究。涉及有机分子的化学反应需要使用试剂和/或催化剂来实现这些转化。目前这些合成工具中最强大的含有过渡金属；虽然效率很高，但这种方法存在成本、实用性、毒性和/或严重的环境影响等显著缺陷。有机硅烷——含有硅的有机分子——缺乏含有过渡金属的有机金属化合物的许多不受欢迎的特性：硅是天然丰富的，因此价格低廉，通常无毒，易于处理，并且很容易以各种功能形式获得。然而，由于缺乏功能性和实用性的试剂和/或催化剂，它们在有机合成中的应用受到限制。目前合成有用的有机硅烷的选择在实用性上是有限的。对于原子转移反应，较温和的试剂，如三烷基硅烷，需要强力活化，而较活泼的试剂，如三烷氧基或三卤硅烷，处理起来比较困难和/或危险。除了少数高活性路易斯酸外，目前还没有硅基催化剂。本提案旨在开发新型硅烷作为有机合成的前沿工具。我们提出，释放有机硅烷作为有机合成中高功能不可或缺的工具的潜力的关键是利用稳定和亚稳定超配位硅烷的力量，我们将通过提案中详细的项目来探索这一想法。正在开发的合成工具将具有很高的价值，使更容易获得不仅影响化学研究而且影响邻近领域（如生物化学、生物学和材料）的重要分子。此外，这项工作不仅扩展了一项单一的技术，而且显著地成熟了合成化学中的一个重要分支领域，即使用硅烷作为强大的、可获得的、廉价的、易于操作的、易于控制的有机试剂和催化剂。我们的实验室将继续探索这一总体思路，以揭示新的反应模式，并激励其他人去追求这些未被充分利用的分子。

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.