Novel types of stable carbenes and their applications

新型稳定卡宾及其应用

• 批准号: 1112133
• 负责人: Guy Bertrand
• 金额: $ 44.4万
• 依托单位: University of California-Riverside
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2011
• 资助国家: 美国
• 起止时间: 2011-07-01 至 2013-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1112133&HistoricalAwards=false
• 关键词: Novel; types; stable; carbenes; their

With the support of the Chemical Synthesis Program of the Chemistry Division, Professor Guy Bertrand of the Chemistry Department at the University of California - Riverside, will prepare several novel classes of carbenes, the isolation of which have been impeded by the belief that they are inherently unstable, or have eluded the synthetic skills of investigators. These species have not only been chosen because they represent exciting synthetic challenges but more importantly because they should feature interesting electronic and steric properties, which can lead to important applications. These carbenes will be used for the activation of small molecules and enthalpically strong bonds, tasks previously exclusive to transition metal complexes. They will also be utilized for the stabilization of radicals and triplet diradicals based on main group elements, especially phosphorus and boron. Imines derived from these carbenes will allow for the preparation of very strong neutral bases and hydride donors, compounds that are of great interest for organic synthesis. These carbenes are original ligands for transition metal catalysts, and over the years the success of homogeneous catalysis can be attributed largely to the development of a diverse range of ligand frameworks that have been used to tune the behavior of the various systems. It is of paramount importance for the future to find catalysts able to transform abundant and cheap molecules into useful compounds ranging from bulk chemicals to therapeutics. The activation of small molecules without transition metal centers offers an alternative paradigm in the continuing search for efficient catalytic systems, and should allow for considerably reducing the cost of important chemical processes. Additionally, this project is at the interface between physical, organic and organometallic chemistry and is therefore well suited to the education of scientists at all levels. The University of California- Riverside, classified as a minority serving institution, is well positioned to provide the highest quality educational experience for students underrepresented in science. Because of this fact, a diverse group of students will be involved in the project. This research will also promote collaborative research and the exchange of undergraduates, and graduates students between UC Riverside and several French universities.

在化学系化学合成项目的支持下，加州大学河滨分校化学系的 Guy Bertrand 教授将制备几种新型卡宾，这些卡宾的分离由于相信它们本质上是卡宾而受到阻碍。不稳定，或者逃避了调查人员的综合技能。选择这些物种不仅是因为它们代表了令人兴奋的合成挑战，更重要的是因为它们应该具有有趣的电子和空间特性，这可以带来重要的应用。这些卡宾将用于激活小分子和强焓键，这是以前过渡金属配合物独有的任务。它们还将用于稳定基于主族元素（尤其是磷和硼）的自由基和三重态双自由基。由这些卡宾衍生的亚胺可以制备非常强的中性碱和氢化物供体，这些化合物对有机合成非常重要。这些卡宾是过渡金属催化剂的原始配体，多年来均相催化的成功很大程度上归功于各种配体框架的发展，这些配体框架已用于调节各种系统的行为。对于未来来说，找到能够将丰富且廉价的分子转化为从大宗化学品到治疗药物等有用化合物的催化剂至关重要。没有过渡金属中心的小分子的活化为持续寻找有效催化系统提供了替代范例，并且应该可以大大降低重要化学过程的成本。此外，该项目处于物理、有机和有机金属化学之间的交叉点，因此非常适合各级科学家的教育。加州大学河滨分校被列为少数族裔服务机构，有能力为科学领域代表性不足的学生提供最高质量的教育体验。因此，不同的学生群体将参与该项目。这项研究还将促进加州大学河滨分校和几所法国大学之间的合作研究以及本科生和研究生的交流。