CAREER: Catalytic Carbene and Nitrene Transfer Reactions by Metalloporphyrins

由无机、生物无机和有机金属化学项目颁发的CAREER奖支持田纳西大学诺克斯维尔分校的Peter Zhang教授对金属卟啉在碳和亚氮转移反应中的催化活性的研究。与氧转移反应相比，金属卟啉的类似碳和亚硝基转移反应尚不发达，但具有重要的基础和应用价值。他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。新的卟啉具有可调的电子，立体和手性环境将通过模块化的方法合成，并将作为辅助配体系统地探测，控制和优化金属卟啉的催化反应活性和选择性。详细的机理研究，包括阐明假定的金属卟啉-碳烯和-亚硝基中间体，将进行了解金属卟啉的催化活性和选择性的起源。希望基于金属卟啉的实际催化系统最终将被开发出来，通过明确定义的碳和亚烯转移过程，选择性地将烯烃和烷烃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教育机会，通过无机，有机，有机金属和仿生方法的结合来解决根本和实际重要的科学问题。拟议的研究将与一系列教育任务相结合。第一，将集中努力指导本科生从事积极的研究项目，特别是妇女、代表性不足的少数民族和主要本科研究所的学生，吸引他们从事化学和有关科学的职业。第二，政府会安排资助各大学的教师到学院的实验室进行研究项目，增加他们的研究和受教育的机会。第三，与建议的研究相关，将为K-12教师/学生和公众开发一个名为“生命的颜色”的教育部分，提高他们对化学科学的认识和兴趣。

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.