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CAREER: Iridium Catalysts for the Activation and Functionalization of Ethereal Substrates

职业：用于以太基质的活化和功能化的铱催化剂

基本信息

批准号：
1847813
负责人：
Nathan Schley
金额：
$ 67.5万
依托单位：
Vanderbilt University
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2019
资助国家：
美国
起止时间：
2019-07-15 至 2025-06-30
项目状态：
未结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1847813&HistoricalAwards=false
关键词：
CAREER Iridium Catalysts Activation Functionalization

项目摘要

Ether molecules are ubiquitous in the chemistry that powers modern society. Simple ethers find applications as solvents, motor fuel additives, and as precursors to polymeric materials such as plastics and epoxies. Complex ethers are used to synthesize carbohydrates required for modern biochemical applications. A defining characteristic of ethers is their low reactivity. However, this useful property limits options for their further chemical modification and thus, usefulness. With support from the Chemical Catalysis program of the National Science Foundation, this research project is developing new catalytic methods to enable ether reactivity. Professor Schley and his group at Vanderbilt University are exploring new methods for ether activation designed to address challenges unique to the utilization of both simple and complex ethers. The team is enriched by strong connections between Vanderbilt and local community colleges in the greater Nashville area. Professor Schley is organizing an outreach program designed to promote undergraduate research opportunities for community college students. Internship opportunities for current or recent community college graduates to conduct summer research at Vanderbilt University are also being created.The stability of the ether functional group with respect to attack by oxidants, strong bases, and nucleophiles is a valuable property in many respects, but limits avenues for direct ether derivatization. As a result, despite the availability, affordability, and low toxicity of simple alkyl ethers, they have been primarily limited to low-value applications. Similarly, the harsh stoichiometric methods used for ether C-O cleavage limits compatibility with complex polyether-containing molecules including carbohydrate derivatives. Through this project the Schley research group is exploring two modes for iridium-mediated electrophilic ether activation involving ether dehydrogenation to electrophilic alkoxycarbenes and ether silylation to give silyloxonium ions. These intermediates are activated towards nucleophilic cleavage reactions of the integral carbon-oxygen bond and represent mechanistically distinct routes to selective, catalytic ether cleavage reactions. This research is being pursued in tandem with outreach to local community colleges in the Nashville area. As a former community college student himself, Professor Schley is piloting an outreach program aimed at disseminating information about undergraduate research opportunities for community college students in Tennessee.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.

醚分子在现代社会的化学中无处不在。简单的醚可用作溶剂、发动机燃料添加剂以及聚合物材料如塑料和环氧树脂的前体。复合醚用于合成现代生物化学应用所需的碳水化合物。醚类的一个决定性特征是它们的低反应性。然而，这种有用的性质限制了它们进一步化学改性的选择，从而限制了它们的有用性。在美国国家科学基金会化学催化计划的支持下，该研究项目正在开发新的催化方法，以实现醚的反应性。范德比尔特大学的Schley教授和他的团队正在探索醚活化的新方法，旨在解决利用简单和复杂醚所面临的独特挑战。范德比尔特和大纳什维尔地区当地社区学院之间的紧密联系丰富了这支球队。Schley教授正在组织一个旨在促进社区大学生本科研究机会的推广计划。目前或最近的社区学院毕业生在范德比尔特大学进行暑期研究的实习机会也正在创造中。醚官能团相对于被氧化剂、强碱和亲核试剂攻击的稳定性在许多方面是有价值的性质，但限制了直接醚衍生化的途径。因此，尽管简单烷基醚的可用性、可负担性和低毒性，但它们主要限于低价值应用。类似地，用于醚C-O裂解的苛刻的化学计量方法限制了与包括碳水化合物衍生物的复杂含聚醚分子的相容性。通过这个项目，Schley研究小组正在探索铱介导的亲电醚活化的两种模式，包括醚脱氢成亲电烷氧基卡宾和醚甲硅烷基化得到硅氧鎓离子。这些中间体被活化朝向完整的碳-氧键的亲核裂解反应，并且代表选择性催化醚裂解反应的机械上不同的路线。这项研究正在与纳什维尔地区的地方社区学院联系起来。作为一个前社区大学的学生自己，教授Schley正在试行一个推广计划，旨在传播有关本科研究的机会，在田纳西州的社区大学的学生的信息。这个奖项反映了NSF的法定使命，并已被认为是值得通过使用基金会的智力价值和更广泛的影响审查标准进行评估的支持。