New Catalysts for Cis-Selective Metathesis: Agostic Interaction and Meso-N-Heterocyclic Carbenes

顺式选择性复分解的新催化剂：不规则相互作用和内消旋-N-杂环卡宾

• 批准号: 0848560
• 负责人: Steven Diver
• 金额: $ 40.5万
• 依托单位: SUNY at Buffalo
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2009
• 资助国家: 美国
• 起止时间: 2009-09-01 至 2012-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=0848560&HistoricalAwards=false
• 关键词: New; Catalysts; Cis; Selective; Metathesis

This project will synthesize new catalysts for cis-selectivity in olefin metathesis. Two new, unexplored approaches will be taken in this project: (1) Use of agostic interactions in early transition metal Fischer carbene complexes to guide selectivity in enyne cross metathesis. In particular, we intend to improve the catalyst stability building upon what we have learned previously in the Diver group while studying enyne metathesis. (2) Building on N-heterocyclic carbene design we will construct an aromatic 'wall' on one side of meso-N-heterocyclic carbenes to control catalyst selectivity in ruthenium carbenes. Currently, the olefin metathesis provides one of the most effective methods for catalytic carbon-carbon double bond construction, and has been widely used by chemists in many fields. Despite the huge success of metathesis chemistry, the major limitation is control of double bond geometry: cis-double bonds cannot be made selectively. This project is focused on this cis-selectivity problem through catalyst development.With this award, the Organic and Macromolecular Chemistry Program is supporting the research of Professor Steven T. Diver of the Department of Chemistry at the State University of New York-Buffalo. Professor Steven Diver's research efforts center on the development of new metathesis methods for the synthesis of rings, the study of the catalytic mechanism of enyne metathesis and the development of new carbene catalysts. This three-pronged effort has impacted our understanding of fundamental aspects of metal carbene reactivity and led to improvements in selectivity in certain synthetic applications. Development of new carbene catalysts is expected to enhance cis-selectivity and lead to a better understanding of which factors are critical to selectivity. Metathesis methods are highly efficient, using small amounts of ruthenium carbene catalysts (known as the Grubbs carbenes) and are widely applicable to the synthesis of small molecules (such as pharmaceuticals) and polymeric structures (such as nanomaterials). Successful development of new catalysts will have an impact on synthesis in the pharmaceutical sector, leading to improved efficiency in drug production.

该项目将合成烯烃元理解中顺式选择性的新催化剂。 该项目将采用两种新的未开发方法：（1）早期过渡金属Fischer Carbene络合物中使用Agostic相互作用来指导Enyne Cross Methathesson中的选择性。 特别是，我们打算在研究Enyne归化的同时，改善我们以前在潜水员组中所学到的知识的催化剂稳定性。 （2）在N-杂环卡宾设计上的建筑物，我们将在Meso-N-杂环卡宾斯的一侧建造一个芳香的“墙”，以控制ruthenium carbenes中的催化剂选择性。目前，烯烃的元解式提供了催化碳碳双键结构的最有效方法之一，并已在许多领域被化学家广泛使用。尽管化学取得了巨大的成功，但主要限制是控制双键几何：不能有选择地制定顺式双键。该项目的重点是通过催化剂开发来解决这一顺式选择性问题。在该奖项的情况下，有机和大分子化学计划正在支持纽约州立大学化学系史蒂文·T·D·斯蒂芬·T·斯蒂芬·T·迪维（Steven T. Diver）的研究。 史蒂文·潜水员（Steven Diver）教授的研究工作中心，开发了综合环的新元方法方法，恩尼·元理解的催化机理以及新卡宾催化剂的发展。 这项三管齐下的努力影响了我们对金属碳反应性基本方面的理解，并导致了某些合成应用中选择性的提高。 预计新的碳烯催化剂将增强顺式选择性，并更好地理解哪些因素对选择性至关重要。使用少量的卡宾催化剂（称为grubbs carbenes）高效效率，并且广泛适用于小分子（例如药物）和聚合物结构（例如纳米材料）的合成。新催化剂的成功开发将对药物领域的合成产生影响，从而提高药物生产效率。