Catalytic, Regioselective Functionalization of Alkane and Arenes

无机化学、生物无机化学和金属有机化学项目的这一奖项支持伊利诺伊大学厄巴纳-香槟分校的约翰·F·哈特威格教授的研究，该研究旨在开发Ir催化的烷烃硼化反应和类似的芳烃与儿茶酚硼烷的硼化反应，以形成更具活性的芳基硼酸酯产品，并对Ir催化的Pinacolborane反应进行机械实验。根据Ru催化剂的初步结果和Ru-B络合物对烷烃的反应活性，将确定在Ru催化的烷烃硼化反应中真正的催化剂，并确定促进C-H键断裂的金属-B络合物的电子性质。在PI最近发现的芳烃硅基化催化剂的基础上，有氢受体和无氢受体的温和的芳烃和烷烃的分子内硅基化反应以及更具活性的芳烃分子间硅基化催化剂将被开发出来。末端C-H键功能化的区域选择性的来源将通过进行一系列的氚标记实验来确定，这些实验将区分C-H键的断裂和B-C键的形成，作为控制烷烃、胺、醚和卤代烷的区域选择性官能化的步骤。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、博士后和博士后的教育经验。作为耶鲁STARS计划的一部分，PI指导了几名少数族裔学生的暑期研究，努力将他的研究展示给高中生团体和其他观众，并参与撰写下一版过渡金属化学教科书。

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.