Metalloradical Catalysis for Selective Radical Reactions

选择性自由基反应的金属自由基催化

• 批准号: 2154885
• 负责人: Peter Zhang
• 金额: $ 52.5万
• 依托单位: Boston College
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2022
• 资助国家: 美国
• 起止时间: 2022-07-01 至 2025-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2154885&HistoricalAwards=false
• 关键词: Metalloradical; Catalysis; Selective; Radical; Reactions

With the support of the Chemical Catalysis program in the Division of Chemistry, Professor Peter Zhang of Boston College is studying metal-based catalytic processes for the environmentally sustainable preparation of organic compounds of utility to science and commerce. Most metal-catalyzed processes rely on so-called "polar reactivity" wherein chemical reactions involve changes of two electrons at a time. Guided by the emerging concept of "metalloradical catalysis" in which changes instead happen one electron at a time, Professor Zhang and his team of coworkers are developing new catalytic systems that take advantage of the unique features of radical reactions. In comparison with the typical need for rare and expensive metals to mediate two-electron polar reactions, the one electron metalloradical reactions of interest are carried out with catalysts based on earth-abundant and inexpensive transition metals such as cobalt. As such, the funded research project addresses important issues of sustainability in fine chemical manufacture and with potential long term benefits for biology, medicine, and materials. The broader impacts of the funded project extend to the promotion of science among the general public by supporting the Zhang group as they provide educational resources for K-12 teachers and stimulate interest in STEM (science, technology, engineering and medicine) conducting outreach activities. As part of these efforts, educational web-based material entitled "The Colors of Life" will be created and made available to the public, and opportunities will be provided for high school students and teachers, as well as undergraduate students, to gain first-hand research experiences in the laboratory.This project focuses on the establishment of metalloradical catalysis as a fundamentally new approach for controlling the reactivity and stereoselectivity of radical reactions. Metalloradical systems based on cobalt(II) complexes of chiral porphyrins will be developed to harness the full potential of homolytic radical chemistry. These new catalytic radical processes, which are both mechanistically distinctive and operationally straightforward, will serve as valuable synthetic tools for the construction of organic compounds, including biologically important natural products and pharmaceutically interesting small molecules. The concept of metalloradical catalysis, which aims at the full exploration of homolysis as a fundamental platform for bond-breaking and -making, will have a far-reaching impact on organic synthesis and it is likely to stimulate the development of further new synthetic methods based on radical chemistry. The further exploration of cobalt-based metalloradical catalysis has the potential to guide the development of new metalloradical catalyst systems based on different combinations of open-shell metal ions and chiral ligands that can catalyze a broad range of stereoselective radical reactions.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

在化学系化学催化项目的支持下，波士顿学院的Peter Zhang教授正在研究金属基催化过程，用于制备对科学和商业有用的有机化合物。大多数金属催化过程依赖于所谓的“极性反应性”，其中化学反应涉及一次两个电子的变化。在“金属自由基催化”这一新兴概念的指导下，张教授和他的同事们正在开发新的催化体系，利用自由基反应的独特功能。与通常需要稀有和昂贵的金属来介导双电子极性反应相比，感兴趣的单电子金属自由基反应是用基于地球上丰富和廉价的过渡金属如钴的催化剂进行的。因此，资助的研究项目解决了精细化学品制造的可持续性的重要问题，并对生物学，医学和材料具有潜在的长期利益。该资助项目的更广泛影响扩展到通过支持张氏集团在公众中推广科学，因为他们为K-12教师提供教育资源，并激发对STEM（科学，技术，工程和医学）进行外展活动的兴趣。作为这些努力的一部分，将制作题为“生活的色彩”的网上教育材料并提供给公众，并将为高中学生和教师以及本科生提供机会，首先获得-本项目的重点是建立金属自由基催化作为控制反应性和立体选择性的一种新方法激进的反应。基于手性卟啉钴（II）配合物的金属自由基体系将被开发，以充分利用均裂自由基化学的潜力。这些新的催化自由基过程，这是机械上独特的和操作简单，将作为宝贵的合成工具的有机化合物，包括生物学上重要的天然产物和药学上有趣的小分子的建设。金属自由基催化的概念旨在充分探索均裂作为键断裂和键生成的基本平台，这将对有机合成产生深远的影响，并可能刺激基于自由基化学的进一步新合成方法的发展。对钴基金属自由基催化的进一步探索有可能指导基于开壳金属离子和手性配体的不同组合的新型金属自由基催化剂体系的开发，该体系可以催化广泛的立体选择性自由基反应。该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

Metalloradical approach for concurrent control in intermolecular radical allylic C−H amination

• DOI: 10.1038/s41557-022-01119-4
• 发表时间: 2023-01
• 期刊: Nature Chemistry
• 影响因子: 21.8
• 作者: Pan Xu;J. Xie;Duo-Sheng Wang;X. Zhang

Asymmetric Radical Bicyclization for Stereoselective Construction of Tricyclic Chromanones and Chromanes with Fused Cyclopropanes.

• DOI: 10.1021/jacs.3c01618
• 发表时间: 2023-05
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: W. Lee;Jingyi Wang;Yiling Zhu;X. Zhang

Electrochemical Diazidation of Alkenes Catalyzed by Manganese Porphyrin Complexes with Second-Sphere Hydrogen-Bond Donors

• DOI: 10.1021/acscatal.2c05186
• 发表时间: 2022-11
• 期刊: ACS Catalysis
• 影响因子: 12.9
• 作者: Luiz F. T. Novaes;Yi Wang;Jinjian Liu;Xavier Riart-Ferrer;Wan-Chen Cindy Lee;Niankai Fu;J. S. Ho;X. Zhang;Song Lin