CAREER: Catalytic Carbene and Nitrene Transfer Reactions by Metalloporphyrins

这项由无机化学、生物无机化学和金属有机化学项目颁发的职业奖支持田纳西诺克斯维尔大学的Peter Zhang教授研究金属卟啉对卡宾和硝烯转移反应的催化反应性。与氧转移反应相比，金属卟啉的类似的卡宾和硝烯转移反应不太发达，但在理论和实践上都很重要。它们产生了有价值的见解，有助于理解相关的生化过程，并为通过C-C和C-N键的形成将廉价和丰富的碳氢化合物转化为增值功能分子的方法提供了模型。以现成的溴卟啉合成子为原料，通过模块化方法合成具有可调电子、空间和手性环境的新型卟啉，并将其用作支持配体，系统地探测、控制和优化金属卟啉的催化活性和选择性。将进行详细的机理研究，包括阐明可能的金属卟啉-卡宾和-硝烯中间体，以了解金属卟啉的催化活性和选择性的来源。基于金属卟啉的实用催化体系有望最终被开发出来，通过明确定义的卡宾和硝烯转移过程，将烯烃和烷烃选择性地转化为更有价值的功能分子。拟议的研究计划的多学科性质为学生提供了一个通过结合无机、有机、有机金属和仿生方法来解决从根本上和实际中的重要科学问题的教育机会。拟议的研究将与一系列教育任务相结合。首先，重点指导积极开展研究项目的本科生，特别是针对女性、代表性不足的少数民族和主要是本科生的学生，吸引他们投身化学及相关科学职业。第二，将安排资助工研院的教职员到工研院的实验室进行研究项目，增加他们的研究和教育机会。第三，将为K-12教师/学生和公众开发一个与拟议研究相关的题为“生命的色彩”的教育部分，以促进他们对化学科学的欣赏和兴趣。

This CAREER award by the Inorganic, Bioinorganic and Organometallic Chemistry program supports work by Professor Peter Zhang at University of Tennessee Knoxville to study catalytic reactivities of metalloporphyrins for carbene and nitrene transfer reactions. In contrast to oxotransfer reactions, the analogous carbene and nitrene transfers by metalloporphyrins are less developed, but are important both fundamentally and practically. They generate valuable insights that aid the understanding of related biochemical processes and provide models for approaches to convert inexpensive and abundant hydrocarbons into value-added functional molecules via C-C and C-N bond formations. New porphyrins with tunable electronic, steric, and chiral environments will be synthesized by a modular approach from readily available bromoporphyrin synthons and will be used as supporting ligands to systematically probe, control, and optimize the catalytic reactivities and selectivities of metalloporphyrins. Detailed mechanistic studies, including elucidation of putative metalloporphyrin-carbene and -nitrene intermediates, will be carried out to understand the origin of catalytic reactivity and selectivity of metalloporphyrins. It is hoped that practical catalytic systems based on metalloporphyrins will ultimately be developed for selective conversions of alkenes and alkanes into more valuable functional molecules via well-defined carbene and nitrene transfer processes.The multidisciplinary nature of the proposed research program provides an edcational opportunity for students to solve fundamentally and practically important scientific problems through a combination of inorganic, organic, organometallic, and biomimetic approaches. The proposed research will be integrated with a range of education missions. First, focused efforts will be made to mentor undergraduate students in active research projects, especially for women, underrepresented minorities, and students from primarily undergraduate institutes (PUIs), attracting them into careers in chemical and related sciences. Second, arrangements will be made to sponsor faculty members at PUIs to conduct research projects in the PI's laboratory, enhancing their research and educational opportunities. Third, an educational component titled "The Colors of Life", which is related to the proposed research, will be developed for K-12 teachers/students and the general public, promoting their appreciation of and interests in chemical science.