Metalloradical Catalysis for Stereoselective Carbene and Nitrene Transfers

立体选择性卡宾和氮烯转移的金属自由基催化

基本信息

  • 批准号:
    1624211
  • 负责人:
  • 金额:
    $ 11.51万
  • 依托单位:
  • 依托单位国家:
    美国
  • 项目类别:
    Standard Grant
  • 财政年份:
    2015
  • 资助国家:
    美国
  • 起止时间:
    2015-08-06 至 2016-05-31
  • 项目状态:
    已结题

项目摘要

With this award from the Chemical Catalysis Program in the Chemistry Division at the National Science Foundation Professor X. Peter Zhang of the University of South Florida will develop metalloradical catalysis and will seek applications for stereoselective radical reactions. Metalloradical catalysis represents a fundamentally new approach for controlling reactivity and selectivity of radical reactions of both C- and N-centered radicals. Stable metalloradicals such as cobalt(II) porphyrin complexes are capable of activating diazo reagents and organic azides to cleanly generate C- and N-centered radicals, respectively, with nitrogen as the only byproduct in a controlled and catalytic manner. The initially formed C- and N-centered radicals, which remain complexed with cobalt(II) porphyrin complexes and are termed as cobalt-carbene and -nitrene radicals, respectively, can undergo common radical reactions such as radical addition and atom abstraction, but with effective control of reactivity and stereoselectivity by the porphyrin ligand environment. Several factors including the low and appropriate bond dissociation energy of Co-C/Co-N bonds are key for the successful turnover of the Co(II)-based catalytic carbene and nitrene transfers. Through the support of porphyrin ligands with tunable electronic, steric, and chiral environments, this general concept of Co(II)-based metalloradical catalysis will be applied for the development of various radical processes, including a number of stereoselective carbene and nitrene transfers.The concept of metalloradical catalysis may have a far-reaching impact in several areas of research, including carbene, nitrene and radical chemistry. Its establishment will stimulate further development of metalloradical catalyst systems with different combinations of open-shell metal ions and chiral ligands for various stereoselective radical reactions, which have a number of inherent synthetic advantages in comparison with ionic reactions. Since metalloradical catalysis can generate radical intermediates catalytically without the need of stoichiometric initiators such as the commonly employed organotin reagents, it will have a positive environmental impact as well. The biological and medical relevance of porphyrin ligands, together with the well demonstrated practical applications of chiral compounds as pharmaceuticals, flavor and aroma chemicals, agricultural chemicals, and specialty materials, will make the planned study an excellent theme to promote science among the general public, to provide education resources for K-12 teachers, and to stimulate scientific interests of K-12 students.
凭借美国国家科学基金会化学部化学催化项目的这一奖项,南佛罗里达大学的 X. Peter 张 教授将开发金属自由基催化,并寻求立体选择性自由基反应的应用。金属自由基催化代表了一种控制以 C 和 N 为中心的自由基的自由基反应的反应性和选择性的全新方法。钴(II)卟啉配合物等稳定的金属自由基能够活化重氮试剂和有机叠氮化物,分别干净地产生以C为中心的自由基和以N为中心的自由基,并以受控和催化的方式将氮作为唯一的副产物。最初形成的C-和N-中心自由基仍与钴(II)卟啉配合物络合,分别称为钴-卡宾和-氮烯自由基,可以进行常见的自由基反应,例如自由基加成和原子夺取,但通过卟啉配体环境有效控制反应性和立体选择性。 Co-C/Co-N 键的低且适当的键解离能等几个因素是 Co(II) 基催化卡宾和氮宾转移成功转换的关键。通过具有可调节电子、空间和手性环境的卟啉配体的支持,这种基于Co(II)的金属自由基催化的一般概念将应用于各种自由基过程的开发,包括许多立体选择性卡宾和氮宾转移。金属自由基催化的概念可能在多个研究领域产生深远的影响,包括卡宾、氮宾和 自由基化学。它的建立将促进开壳金属离子和手性配体不同组合的金属自由基催化剂体系的进一步发展,用于各种立体选择性自由基反应,与离子反应相比,其具有许多固有的合成优势。由于金属自由基催化可以催化生成自由基中间体,而不需要化学计量引发剂(例如常用的有机锡试剂),因此它也会对环境产生积极的影响。卟啉配体的生物学和医学相关性,以及手性化合物在药物、香料和芳香化学品、农用化学品和特种材料等领域的实际应用,将使该计划的研究成为在公众中推广科学、为 K-12 教师提供教育资源并激发 K-12 学生的科学兴趣的绝佳主题。

项目成果

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Peter Zhang其他文献

Brexpiprazole as adjunctive treatment of major depressive disorder with anxious distress: Results from a post-hoc analysis of two randomised controlled trials.
布雷哌唑作为伴有焦虑困扰的重度抑郁症的辅助治疗:两项随机对照试验的事后分析结果。
  • DOI:
  • 发表时间:
    2016
  • 期刊:
  • 影响因子:
    6.6
  • 作者:
    R. McIntyre;E. Weiller;Peter Zhang;C. Weiss
  • 通讯作者:
    C. Weiss
PO-03-177 VEIN OF MARSHALL ETHANOL ABLATION AS A STRATEGY FOR RECURRENT PERSISTENT ATRIAL FIBRILLATION
马歇尔静脉乙醇消融术作为治疗复发性持续性心房颤动的策略(PO-03-177)
  • DOI:
    10.1016/j.hrthm.2025.03.1087
  • 发表时间:
    2025-04-01
  • 期刊:
  • 影响因子:
    5.700
  • 作者:
    Brian Hsia;Peter Zhang;Joey Junarta;Leonid Garber;Felix Yang;Michael A. Spinelli;Yury Malyshev;Alexander Kushnir;Lior Jankelson;Scott A. Bernstein;David S. Park;Chirag R. Barbhaiya;Douglas Holmes;Larry A. Chinitz;Anthony Aizer
  • 通讯作者:
    Anthony Aizer
Cilostazol Treatment of Claudication in Diabetic Patients
西洛他唑治疗糖尿病患者跛行
Dipole model of vorticity at the moving contact line
动接触线处涡量的偶极子模型
Roof Stability and Support Strategies Associated with Longwall-induced Horizontal Stress Changes in Belt Entries
  • DOI:
    10.1007/s42461-022-00634-9
  • 发表时间:
    2022-06-14
  • 期刊:
  • 影响因子:
    2.000
  • 作者:
    Peter Zhang;Gabriel Esterhuizen;Morgan Sears;Jack Trackemas;Todd Minoski;Berk Tulu
  • 通讯作者:
    Berk Tulu

Peter Zhang的其他文献

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{{ truncateString('Peter Zhang', 18)}}的其他基金

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
  • 财政年份:
    2022
  • 资助金额:
    $ 11.51万
  • 项目类别:
    Standard Grant
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:
    1900375
  • 财政年份:
    2019
  • 资助金额:
    $ 11.51万
  • 项目类别:
    Standard Grant
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:
    1465106
  • 财政年份:
    2015
  • 资助金额:
    $ 11.51万
  • 项目类别:
    Standard Grant
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:
    1624216
  • 财政年份:
    2015
  • 资助金额:
    $ 11.51万
  • 项目类别:
    Standard Grant
Metalloradical Catalysis for Stereoselective Carbene and Nitrene Transfers
立体选择性卡宾和氮烯转移的金属自由基催化
  • 批准号:
    1152767
  • 财政年份:
    2012
  • 资助金额:
    $ 11.51万
  • 项目类别:
    Standard Grant
CAREER: Catalytic Carbene and Nitrene Transfer Reactions by Metalloporphyrins
职业:金属卟啉催化卡宾和氮烯转移反应
  • 批准号:
    0711024
  • 财政年份:
    2006
  • 资助金额:
    $ 11.51万
  • 项目类别:
    Continuing Grant
CAREER: Catalytic Carbene and Nitrene Transfer Reactions by Metalloporphyrins
职业:金属卟啉催化卡宾和氮烯转移反应
  • 批准号:
    0547930
  • 财政年份:
    2006
  • 资助金额:
    $ 11.51万
  • 项目类别:
    Continuing Grant

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不对称Tandem catalysis 合成手性仲醇
  • 批准号:
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新型催化剂的开发实现催化剂控制的立体选择性自由基聚合
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