Catalytic, Regioselective Functionalization of Alkane and Arenes

烷烃和芳烃的催化、区域选择性官能化

• 批准号: 0653335
• 负责人: John Hartwig
• 金额: $ 49.4万
• 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: 2006-08-01 至 2009-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0653335&HistoricalAwards=false
• 关键词: Catalytic; Regioselective; Functionalization; Alkane; Arenes

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor John F. Hartwig at theUniversity of Illinois at Urbana-Champaign to develop an iridium-catalyzed borylation of alkanes and a similar borylation of arenes with catecholborane to form more reactive arylboronate products and to conduct mechanistic experiments on iridium-catalyzed reactions of pinacolborane. Based on preliminary results gained with ruthenium catalysts and the reactivity of ruthenium boryl complexes toward alkanes, the true catalyst in the ruthenium-catalyzed borylation of alkanes will be identified and the electronic properties of metal-boryl complexes that promote C-H bond cleavage will be determined. Based on the PI's recent discovery of catalysts for the silylation of arenes, mild intramolecular silylations of arenes and alkanes with and without a hydrogen acceptor and more reactive catalysts for the intermolecular silylation of arenas will be developed. The origins of the regioselectivity for functionalization of terminal C-H bonds will be determined by conducting a series of deuterium labeling experiments that will distinguish between C-H bond cleavage and B-C bond formation as the step that controls regioselective functionalization of alkanes, amines, ethers and haloalkanes. The work described here will extend new methods of catalysis and help broaden the educational experiences of undergraduate, PhD and postdoctoral students. The PI mentors the summer research of several minority students as part of Yale's STARS program, endeavors to present his research to groups of high school students and other audiences, and is involved in writing the next edition of a textbook on transition metal chemistry.

This award in the Inorganic, Bioinorganic and Organometallic Chemistry program supports research by Professor John F. Hartwig at theUniversity of Illinois at Urbana-Champaign to develop an iridium-catalyzed borylation of alkanes and a similar borylation of arenes with catecholborane to form more reactive arylboronate products and to conduct mechanistic experiments on iridium-catalyzed Pinacolborane的反应。 基于用氟苯催化剂获得的初步结果，以及芳族对烷烃的反应性，将确定将确定烷基烷烃的真正催化剂，并确定促进C-H键裂解的金属伴侣复合物的电子特性。 基于PI最近发现的用于竞技场的催化剂，将开发带有和没有氢受体的竞技场和烷烃的轻度分子内硅烷基，并且将开发出更大的反应性催化剂，以用于竞技场的分子丝丝化。末端C-H键功能化的区域选择性的起源将通过进行一系列氘标记实验来确定，该实验将区分C-H键裂解和B-C键形成，作为控制烷烃的区域性功能化的步骤，胺，Ethers和Haloalkanes。此处描述的工作将扩展新的催化方法，并有助于扩大本科，博士和博士后学生的教育经验。 PI指导了几名少数族裔学生的夏季研究，这是耶鲁大学明星计划的一部分，努力向高中生和其他受众群体介绍他的研究，并参与撰写下一版的有关过渡金属化学教科书。