New Approaches to Catalysis: Dual Nucleophilic/Transition Metal Catalysis and Bimetallic Cu Catalysts for Oxidative Functionalizations

催化新方法：双亲核/过渡金属催化和用于氧化功能化的双金属铜催化剂

• 批准号: RGPIN-2014-05988
• 负责人: Lundgren, Rylan
• 金额: $ 2.84万
• 依托单位: University of Alberta
• 依托单位国家: 加拿大
• 项目类别: Discovery Grants Program - Individual
• 财政年份: 2015
• 资助国家: 加拿大
• 起止时间: 2015-01-01 至 2016-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=588736
• 关键词: New; Approaches; Catalysis; Dual; Nucleophilic

Catalysis plays an enormous role in the synthesis and production of nearly all chemicals. Close to 10 trillion dollars of gross world product are directly reliant upon some type of catalytic process. Studies directed towards the development of new homogeneous catalytic species and reaction pathways have made a major impact on virtually all areas of chemistry and its ancillary fields (biology, materials science, drug discovery, etc.) However, despite the remarkable advances made in the area of homogeneous catalysis, many conceptually simple and potentially revolutionary chemical transformations remain out of reach. It is the overarching goal of our research group to develop new catalysts and chemical reactivity to provide solutions to challenges in modern chemistry. In order to develop new and useful reactivity, we have identified two core areas of study we intend to focus upon. One area centralizes around the hypothesis that N-heterocyclic carbene (NHC) activation of electrophiles can be merged with simultaneous substrate activation by late transition metals, such as Au, Pd, Ru, and Ir. We will use this powerful principle to develop a number of important chemical transformations. Such examples include: 1. The NHC/transition metal catalyzed allylic functionalization of aldehydes; 2. The NHC/Au-catalyzed intermolecular hydroacylation of simple alkenes; and 3. The development of "programmable" Benzoin condensation reactions via NHC activation and transition metal catalyzed dehydrogenation/hydrogen transfer. In each case, exquisite control over chemo-, regio-, and enantioselectivity can be achieved by proper selection of catalyst components. A second area of research we will pursue is the concept of bimolecularity as a strategy to enable improved or novel Cu-catalyzed oxidative functionalizations. We will develop two branches of bimetallic Cu-containing catalysts: one aimed to promote organometallic oxidase activity and allow, for example, the oxidative coupling of arenes and ketones; and a second aimed at mimicking the reactivity of dicopper hydroxylating enzymes to enable selective sp3 C-H bond oxidative hetero-functionalizations. The concepts and the knowledge we develop will allow for new reactivity with simple and abundant substrates, such as alkenes, aldehydes, alcohols, and C-H bonds, all of which will have significant impact on chemical synthesis.

催化作用在几乎所有化学物质的合成和生产中起着巨大的作用。近10万亿美元的世界生产总值直接依赖于某种类型的催化过程。针对开发新的均相催化物质和反应途径的研究对化学及其附属领域（生物学、材料科学、药物发现等）的几乎所有领域都产生了重大影响。然而，尽管均相催化领域取得了显著进展，但许多概念上简单且具有潜在革命性的化学转化仍然遥不可及。我们研究小组的首要目标是开发新的催化剂和化学反应性，为现代化学中的挑战提供解决方案。