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

职业：催化有机过渡金属化学：通过烯丙基 C-H 键活化形成 C-C 键的反应

• 批准号: 0548173
• 负责人: M. Christina White
• 金额: $ 47.5万
• 依托单位: University of Illinois at Urbana-Champaign
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2006
• 资助国家: 美国
• 起止时间: 2006-03-01 至 2011-02-28
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0548173&HistoricalAwards=false
• 关键词: CAREER; Catalytic; Organotransition; Metal; Chemistry

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.

有了这个职业奖从有机和高分子化学计划，教授M。伊利诺伊大学厄巴纳-尚潘分校化学系的克里斯蒂娜白色将开发催化有机过渡金属方法，将惰性烃分子转化为功能复杂的产品。本提案中所述研究的目的是开发和机理研究用于实现α-烯烃分子烷基化的高选择性催化方法。α-烯烃的烯丙基烷基化以前仅可能通过钯金属中化学计量的多步路线。与使这样的方法具有催化性相关的挑战是发现在烷基化试剂存在下实现烯丙基C-H裂解步骤所需的亲电Pd（II）催化剂的负载和再生条件。将这些反应添加到有机化学工具箱中将简化生物重要化合物的合成。此外，这些反应的机理研究有助于为有机过渡金属化学领域的催化剂设计和化学反应性提供新的原则。在化学系有机和高分子化学项目的支持下，白色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。一个有机过渡金属化学研讨会和网站的发展，提出了一个不同的目标，暴露一组有才华的本科生在化学这个强大的主题。两个历史上的黑人大学（HBCU）将作为现场和网络版本的研讨会的试验台。默克制药公司的一位工业科学家将在研讨会上发表演讲，介绍催化有机过渡金属化学在工业中的影响。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追求化学的高级学位和职业，从而扩大化学领域的年轻人才库。