SusChEM: Selective C-H Functionalization by Highly Tunable Metalloporphyrin Carbenoid: A Mechanistic Investigation

SusChEM：高度可调金属卟啉类胡萝卜素选择性 C-H 官能化：机理研究

• 批准号: 1300912
• 负责人: Yong Zhang
• 金额: $ 33万
• 依托单位: Stevens Institute of Technology
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-06-01 至 2018-05-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1300912&HistoricalAwards=false
• 关键词: SusChEM; Selective; Functionalization; Highly; Tunable

The Division of Chemistry supports the efforts of Professor Yong Zhang of the Stevens Institute of Technology towards selective carbon-hydrogen (C-H) functionalization using metalloporphyrin carbenoids. Metalloporphyrin carbenoids have been found to be among the most efficient and selective catalysts for C-H insertions however, mechanistic studies on these catalysts are relatively scarce and the origins of molecular reactivity and selectivity have not been well characterized. Such information is critical for the future development of these catalysts, especially since most reported C-H insertion yields are modest. Dr. Zhang's research provides systematic profiles of the origins of reactivity for key metalloporphyrin carbenes as well as reactivity and selectivity trends of various structural factors to facilitate the development of highly selective metalloporphyrin-based C-H insertion catalysts with metal centers that are earth-abundant, minimally toxic, and relatively inexpensive. Dr. Zhang's research is broadly integrated with teaching and learning. Students in his lab are actively involved in classes and outreach programs that incorporate their research results. Dr. Zhang continues his vigorous efforts to have broad participation of students from different groups at various levels, particularly including students from underrepresented groups. Organic synthesis is of vital importance in modern society to provide drugs and materials. Selective carbon-hydrogen (C-H) functionalization represents a powerful, potentially sustainable strategy for organic synthesis. As models of broadly interesting and useful heme protein reaction intermediates, metalloporphyrin carbenoids have been found to be among the most efficient and highly selective catalysts for C-H insertions into organic molecules, even though few mechanistic studies have been done and their origin of the catalyst's reactivity and selectivity are not clear. Such information is critical for future development, especially since most C-H insertion yields using these catalysts are modest. Dr. Zhang's research provides systematic profiles of needed information such as molecular design guidelines to facilitate the development of highly selective metalloporphyrin-based C-H insertion catalysts that use earth-abundant metals (such as iron). Such insights may lead to improvements sustainable and "green" chemistry in the pharmaceutical and materials syntheses industries. Dr. Zhang's research is broadly integrated with teaching and learning. Several channels are employed by his students to broadly disseminate their research to the scientific community and general public. For example, students involved in this NSF-supported project are required to give presentations/reports in their classes, and within their department, university, K-12 institutions, museums, news media, and/or other venues, enhancing the scientific understanding of the impacts of this project.

化学系支持史蒂文斯理工学院张勇教授利用金属卟啉类胡萝卜素选择性碳氢（C-H）功能化的努力。 金属卟啉类胡萝卜素已被发现是最有效和最具选择性的 C-H 插入催化剂之一，然而，对这些催化剂的机理研究相对较少，并且分子反应性和选择性的起源尚未得到很好的表征。 这些信息对于这些催化剂的未来发展至关重要，特别是因为大多数报道的 C-H 插入产率并不高。 张博士的研究系统地描述了关键金属卟啉卡宾的反应性起源以及各种结构因素的反应性和选择性趋势，以促进高选择性金属卟啉基C-H插入催化剂的开发，该催化剂具有地球丰富的、最低限度的金属中心有毒，且相对便宜。 张博士的研究广泛地与教学相结合。 他实验室的学生积极参与融入他们研究成果的课程和推广项目。 张博士继续积极努力让不同群体、不同层次的学生，特别是弱势群体的学生广泛参与。 有机合成对于现代社会提供药物和材料至关重要。 选择性碳氢（C-H）官能化代表了一种强大的、潜在可持续的有机合成策略。 作为广泛有趣和有用的血红素蛋白反应中间体的模型，金属卟啉类胡萝卜素已被发现是 C-H 插入有机分子的最有效和高选择性的催化剂之一，尽管很少进行机械研究以及催化剂反应性和起源的研究。选择性不明确。 这些信息对于未来的发展至关重要，特别是因为使用这些催化剂的大多数 C-H 插入产率都很有限。 张博士的研究提供了所需信息的系统概况，例如分子设计指南，以促进使用地球丰富的金属（例如铁）的高选择性金属卟啉基 C-H 插入催化剂的开发。 这些见解可能会改善制药和材料合成行业的可持续和“绿色”化学。 张博士的研究广泛地与教学相结合。 他的学生利用多种渠道向科学界和公众广泛传播他们的研究成果。 例如，参与该 NSF 支持项目的学生需要在课堂上以及所在院系、大学、K-12 机构、博物馆、新闻媒体和/或其他场所进行演示/报告，以增强对以下内容的科学理解：该项目的影响。

项目成果

Biocatalytic Intramolecular C−H aminations via Engineered Heme Proteins: Full Reaction Pathways and Axial Ligand Effects

通过工程血红素蛋白进行生物催化分子内 C–H 胺化：完整反应途径和轴向配体效应

• DOI: 10.1002/chem.202202006
• 发表时间: 2022-10-21
• 期刊: Chemistry – A European Journal
• 作者: Wei, Yang;Conklin, Melissa;Zhang, Yong
• 通讯作者: Zhang, Yong