Novel types of stable carbenes and their applications

新型稳定卡宾及其应用

• 批准号: 1316956
• 负责人: Guy Bertrand
• 金额: $ 40.52万
• 依托单位: University of California-San Diego
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2012
• 资助国家: 美国
• 起止时间: 2012-07-01 至 2014-06-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1316956&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.

在化学系化学合成计划的支持下，加州大学河滨分校化学系的盖伊·伯特朗教授将准备几类新的卡宾，这些卡宾的分离因认为它们天生不稳定而受阻，或躲避了研究人员的合成技能。选择这些物种不仅是因为它们代表着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性质，这可能会导致重要的应用。这些卡宾将用于激活小分子和热强键，这是以前过渡金属络合物所独有的任务。它们还将用于稳定基于主族元素的自由基和三重双自由基，特别是磷和硼。从这些卡宾衍生的亚胺将允许制备非常强的中性碱和氢化物给体，这些化合物对有机合成非常感兴趣。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在很大程度上可以归功于各种配体框架的发展，这些框架已被用于调整各种体系的行为。对于未来来说，找到能够将丰富而廉价的分子转化为从大宗化学品到治疗药物的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继续寻找有效的催化体系提供了一种替代范式，并应允许显著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的交界处，因此非常适合各级科学家的教育。加州大学河滨分校被归类为少数族裔服务机构，它处于有利地位，可以为在科学领域代表性不足的学生提供最高质量的教育体验。由于这一事实，不同的学生群体将参与到这个项目中来。这项研究还将促进加州大学河滨分校与几所法国大学之间的合作研究和本科生和研究生的交流。