CAREER: Catalytic Carbene and Nitrene Transfer Reactions by Metalloporphyrins

这项由无机，生物无机和有机化学计划颁发的职业奖支持田纳西大学诺克斯维尔的Peter Zhang教授研究金属卟啉对卡宾和氮烯转移反应的催化反应性的工作。与氧代转移反应相比，金属卟啉的类似卡宾和氮烯转移反应发展较少，但在基础和实践上都很重要。它们产生了有价值的见解，有助于理解相关的生物化学过程，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。新的卟啉与可调的电子，空间和手性环境将合成一个模块化的方法，从现成的溴卟啉双离子，并将被用作支持配体系统地探测，控制和优化金属卟啉的催化反应性和选择性。详细的机理研究，包括阐明假定的金属卟啉-卡宾和-氮烯中间体，将进行了解金属卟啉的催化反应性和选择性的起源。希望基于金属卟啉的实用催化体系最终将被开发用于通过明确的卡宾和氮烯转移过程将烯烃和烷烃选择性转化为更有价值的功能分子。拟议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。拟议的研究将与一系列教育任务相结合。首先，将集中精力指导积极研究项目的本科生，特别是女性，代表性不足的少数民族和主要本科院校的学生，吸引他们进入化学和相关科学的职业生涯。第二，我们会安排资助专业进修学院的教职员在专业进修学院的实验室进行研究计划，以增加他们进行研究和接受教育的机会。第三，为幼儿园至12年级的教师/学生及公众，发展一个与拟议研究有关的教育部分，名为“生命的色彩”，以提高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.