CAREER: Stereoselective manipulation of unstabilized carbocations

通过这一职业奖项，化学合成项目正在支持斯克里普斯研究所化学系的Ryan A.Shenvi博士的研究和教育努力。这项研究的重点是开发一类新的立体选择性亲核置换反应，通过不稳定的碳阳离子接触离子对的攻击来操作孤立的叔碳中心。这项研究填补了近100年来化学合成中的一个主要方法学空白。这一提议的目标的实现将广泛影响具有挑战性的叔烷基取代手性材料的合成，这些手性材料很难或不可能通过其他方法获得。这项研究的一个成功结果是不稳定的碳正离子与各种亲核试剂的反应具有很高的化学和立体选择性，这对生物、医学和物理领域的界面材料的生产具有重要的影响。这项研究的关键重点是通过发明新的化学反应来开发简明和可扩展的治疗相关分子的合成，这种合成允许一定程度的复杂性，这是标准方法无法实现的。拟议的研究可能会使人们能够随时获得一些重要的天然和非天然产品，同时减少步骤和提高效率。这笔赠款的教育部分包括课程开发和通过斯克里普斯冲浪计划的推广。这一努力包括为高中、本科生和研究生教育开发一门课程，在有机化学研究的背景下阐明科学方法。

With this CAREER award, the Chemical Synthesis Program is supporting the research and educational efforts of Dr. Ryan A. Shenvi of the Department of Chemistry at the Scripps Research Institute. The focus of this research is to develop a new class of stereoselective nucleophilic displacement reactions that operate on isolated tertiary carbon centers through attack of unstabilized carbocationic contact ion pairs. This research fills a major methodological gap in chemical synthesis that has been recognized for nearly 100 years. Realization of the goals of this proposal would broadly impact the synthesis of challenging tert-alkyl-substituted chiral materials that are difficult or impossible to access by other methods. A successful outcome of the research proposed here entails the reaction of unstabilized carbocations and various nucleophiles with high chemo- and stereoselectivity, which has important consequences for the production of materials for the interfacing fields of biology, medicine, and physics.The key focus of this research is on the development of concise and scalable syntheses of therapeutically relevant molecules through the invention of new chemical reactions that allow a degree of complexity which has been unachievable through standard methods. The proposed research will potentially allow ready access to a number of important natural and unnatural products while reducing the number of steps and increasing the efficiency. The educational component of this grant involves curriculum development and outreach through the Scripps SURF program. This effort involves the development of a curriculum for high-school, undergraduate, and graduate education that articulates the scientific method in the context of organic chemistry research.