CAREER: Catalytic Organotransition Metal Chemistry: C-C Bond Forming Reactions via Allylic C-H Bond Activation

伊利诺伊大学厄巴纳-香槟分校化学系的M.Christina White教授获得了有机化学和高分子化学项目颁发的这一职业奖，他将开发催化有机过渡金属方法，将惰性碳氢分子转化为功能复杂的产品。本建议所述研究的目的是开发高选择性、催化α-烯烃分子烷基化的方法并对其进行机理研究。在此之前，α-烯烃的烯丙烷基化只能通过钯金属中化学计量比的多步路线来实现。与使这些过程催化相关的挑战是发现在烷基化试剂存在的情况下实现烯丙基C-H裂解步骤所需的支持和再生亲电Pd(II)催化剂的条件。将这些反应添加到有机化学家工具箱中将简化具有生物意义的化合物的合成。此外，对这些反应的机理研究将为有机过渡金属化学领域的催化剂设计和化学反应活性提供新的原理。在化学系有机和高分子化学项目的支持下，怀特教授将利用有机过渡金属化学的基本原理来设计解决有机合成中具有挑战性的问题的策略。开发有机过渡金属化学研讨会和网站的目的是为了让不同的有才华的本科生群体接触到这个强大的化学主题。两所历史悠久的黑人大学(HBCU)将作为研讨会现场和网络版本的试验台。默克制药的一位工业科学家将在研讨会上就催化有机过渡金属化学在工业中所产生的影响发表演讲。接触现代有机化学的前沿研究课题将激励来自不同背景的有才华的学生在化学领域追求更高的学位和职业，从而扩大化学领域的年轻人才库。

With this CAREER award from the Organic and Macromolecular Chemistry Program, Professor M. Christina White, of the Department of Chemistry at the University of Illinois-Urbana-Champaign, will develop catalytic organotransition metal methods for converting inert hydrocarbon molecules into functionally complex products. The aim of the research described in this proposal is the development and mechanistic study of highly selective, catalytic methods for effecting alkylation of alpha-olefin molecules. Allylic alkylation of alpha-olefins has previously only been possible via multi-step routes that are stoichiometric in palladium metal. The challenges associated with making such processes catalytic are discovering conditions that will support and regenerate the electrophilic Pd(II) catalyst required to effect the allylic C-H cleavage step in the presence of an alkylating reagent. The addition of these reactions to the organic chemist toolbox will streamline the synthesis of biologically significant compounds. Moreover, the mechanistic study of these reactions stands to contribute new principles of catalyst design and chemical reactivity to the field of organotransition metal chemistry. With the support of the Organic and Macromolecular Chemistry Program in the Chemistry Division, Professor White will use fundamental principles of organotransition metal chemistry to devise strategies to solve challenging problems in organic synthesis. The development of an Organotransition Metal Chemistry Workshop and website is proposed with the objective of exposing a diverse group of talented undergraduate students to this powerful topic in chemistry. Two historically black colleges (HBCUs) will serve as test beds for the on-site and web-based versions of the workshop. An industrial scientist from Merck Pharmaceuticals will present a lecture in the workshop on the impact that catalytic organotransition metal chemistry has made in industry. Exposure to frontier research topics in modern organic chemistry will inspire talented students from diverse backgrounds to pursue advanced degrees and careers in chemistry thereby expanding the pool of young talent in the field of chemistry.