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.

这个奖项在无机，生物无机和有机化学计划支持研究教授约翰F。Hartwig在伊利诺伊大学厄巴纳-香槟分校进行了铱催化的烷烃硼化反应和芳烃与儿茶酚硼烷的类似硼化反应，以形成更具反应性的芳基硼酸酯产物，并对铱催化的频哪醇硼烷反应进行了机理实验。 基于钌催化剂和钌硼基络合物对烷烃的反应性所获得的初步结果，将确定在铼催化的烷烃硼基化反应中的真正催化剂，并确定促进C-H键断裂的金属硼基络合物的电子性质。 基于PI最近发现的芳烃甲硅烷基化催化剂，将开发芳烃和烷烃的温和分子内甲硅烷基化（有和没有氢受体）和芳烃分子间甲硅烷基化的更具反应性的催化剂。末端C-H键官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，所述氘标记实验将区分C-H键裂解和B-C键形成，作为控制烷烃、胺、醚和卤代烷烃的区域选择性官能化的步骤。这里描述的工作将扩展新的催化方法，并有助于拓宽本科生，博士和博士后学生的教育经验。PI指导几个少数民族学生的夏季研究作为耶鲁大学的明星计划的一部分，努力向高中生和其他观众群体介绍他的研究，并参与编写过渡金属化学教科书的下一版。