SusChEM: Magnesium-catalyzed hydrosilylation and hydroboration for efficient carbon-silicon and carbon-boron bond formation

SusChEM：镁催化的硅氢化和硼氢化反应可有效形成碳-硅和碳-硼键

• 批准号: 1464774
• 负责人: Aaron Sadow
• 金额: $ 56万
• 依托单位: Iowa State University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-07-01 至 2019-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1464774&HistoricalAwards=false
• 关键词: SusChEM; Magnesium; catalyzed; hydrosilylation; hydroboration

In this project funded by the Chemical Catalysis program of the Chemistry Division, Professor Aaron Sadow of Iowa State University is developing new catalytic reactions to construct complex systems. The products of these reactions are reagents commonly used as synthetic intermediates for materials and fine chemical technologies. Current processes to create important synthetic intermediates often generate significant quantities of waste or employ expensive metals. The catalysts being studied in this project are instead based on abundant magnesium, calcium or zinc compounds. This chemistry should yield catalytic processes with greater efficiency, reduced demand for precious metals, and diversified synthetic routes to important compounds. Professor Sadow is also studying the reaction mechanisms and the factors that control the chemistry of the catalytic reactions, which will help to optimize the outcomes of the catalysis and to add to fundamental knowledge of the chemistry. Additionally, outreach activities are being pursued to disseminate information on chemical sustainability to public audiences through university and public seminar series. Graduate and undergraduate students are receiving broad training in chemical synthesis, characterization, mechanistic study, and molecular design, which are important for success in any scientific problem-solving endeavor related to catalysis.Professor Sadow is studying the catalytic conversion of oxygen-containing organic molecules. Early transition-metal alkoxides do not readily transfer to weak electrophiles such as silanes due to limiting factors of the strong, polar metal-oxygen bonds in these compounds. The transfer of alkyl groups from main group metal compounds, such as Grignard reagents, is well established and useful in synthetic chemistry for silicon-carbon and boron-carbon bond formations. Instead, the limitations on magnesium-carbon bond formations hinder the application of facile alkyl group transfer reactions in catalytic transformations that employ main group metal catalysts. Professor Sadow is studying group transfer reactions centered on magnesium and calcium, along with related oxophilic metal centers. These studies are being accomplished through the development of early-metal catalytic sites and reagents to efficiently and selectively transform oxygenates as well as through kinetic studies of organoelement bond formations involving group transfer from oxophilic main group metal centers. The work involves the synthesis of main group metal complexes with ligand environments that labilize strong metal-element bonds and while stabilizing reactive intermediates.

在这项由化学系化学催化计划资助的项目中，爱荷华州立大学的亚伦·萨杜教授正在开发新的催化反应来构建复杂的体系。这些反应的产物是通常用作材料和精细化工技术的合成中间体的试剂。目前生产重要合成中间体的工艺往往产生大量废物或使用昂贵的金属。相反，本项目研究的催化剂是基于丰富的镁、钙或锌化合物。这种化学应该会产生效率更高的催化过程，减少对贵金属的需求，并使合成重要化合物的路线多样化。Sadow教授还在研究催化反应的反应机理和控制化学的因素，这将有助于优化催化结果并增加化学基础知识。此外，正在开展外联活动，通过大学和公共研讨会系列向公众传播有关化学品可持续性的信息。研究生和本科生正在接受化学合成、表征、机械研究和分子设计方面的广泛培训，这些对成功解决与催化有关的任何科学问题都很重要。萨杜教授正在研究含氧有机分子的催化转化。由于过渡金属化合物中的强极性金属-氧键的限制因素，早期过渡金属醇氧化物不容易转移到诸如硅烷之类的弱亲电性上。从主族金属化合物，如格氏试剂，转移烷基是公认的，并在合成化学中用于硅-碳和硼-碳键的形成。相反，镁碳键形成的限制阻碍了简单的烷基转移反应在使用主族金属催化剂的催化转化中的应用。Sadow教授正在研究以镁和钙为中心的基团转移反应，以及相关的亲氧金属中心。这些研究是通过开发早期金属催化中心和试剂来高效和选择性地转化含氧化合物，以及通过涉及亲氧主族金属中心基团转移的有机元素键形成的动力学研究来完成的。这项工作包括合成具有配体环境的主族金属络合物，这些络合物可以稳定强金属-元素键，同时稳定活性中间体。