Catalytic, Regioselective Functionalization of Alkane and Arenes

这个无机、生物无机和有机金属化学项目的奖项支持伊利诺伊大学厄巴纳-香槟分校的John F. Hartwig教授的研究，以开发一种铱催化的烷烃硼化反应，以及一种类似的芳烃与儿儿酚硼烷的硼化反应，以形成更活泼的芳基硼酸盐产品，并对铱催化的蒎烷硼烷反应进行机理实验。基于钌催化剂的初步结果和钌硼基配合物对烷烃的反应活性，将确定钌催化烷烃硼化反应的真正催化剂，并确定促进C-H键裂解的金属硼基配合物的电子性质。在PI最近发现的芳烃硅基化催化剂的基础上，将开发具有或不具有氢受体的芳烃和烷烃的轻度分子内硅基化，以及更多的芳烃分子间硅基化反应催化剂。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，这些实验将区分C-H键的裂解和B-C键的形成，作为控制烷烃、胺、醚和卤代烷区域选择性功能化的步骤。这里描述的工作将扩展催化的新方法，并有助于拓宽本科生、博士和博士后的教育经验。作为耶鲁STARS项目的一部分，他指导了几名少数民族学生的暑期研究，努力向高中生和其他观众展示他的研究成果，并参与编写过渡金属化学教科书的下一版。

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.