CAREER: Stereoselective manipulation of unstabilized carbocations

有了这个职业奖，化学合成计划是支持博士的研究和教育工作。斯克里普斯研究所化学系的申维说。 本研究的重点是开发一类新的立体选择性亲核取代反应，通过攻击不稳定的碳阳离子接触离子对操作孤立的叔碳中心。这项研究填补了近100年来公认的化学合成中的一个主要方法学空白。该提案目标的实现将广泛影响具有挑战性的叔烷基取代的手性材料的合成，这些材料难以或不可能通过其他方法获得。这里提出的研究的成功结果需要不稳定的碳阳离子和各种亲核试剂以高化学和立体选择性进行反应，这对生物学，医学，这项研究的重点是通过发明新的化学反应，允许一定程度的复杂性，这是通过标准方法无法实现的。拟议的研究将有可能使许多重要的天然和非天然产品，同时减少步骤的数量和提高效率。 这项赠款的教育部分涉及通过斯克里普斯次区域资源中心方案制定课程和推广活动。这项工作涉及高中，本科和研究生教育的课程，阐明了有机化学研究的背景下的科学方法的发展。

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.