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: 2018
• 资助国家: 加拿大
• 起止时间: 2018-01-01 至 2019-12-31
• 项目状态: 已结题
• 来源: https://www.nserc-crsng.gc.ca/ase-oro/Details-Detailles_eng.asp?id=658097
• 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.

催化在几乎所有化学品的合成和生产中发挥着巨大作用。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。旨在开发新的均相催化物种和反应途径的研究几乎对化学及其辅助领域（生物学、材料科学、药物发现等）的所有领域产生了重大影响。然而，尽管该领域取得了显着的进步对于均相催化，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。我们研究小组的总体目标是开发新的催化剂和化学反应性，为现代化学的挑战提供解决方案。**为了开发新的有用的反应性，我们确定了我们打算重点关注的两个核心研究领域。其中一个领域集中于这样一种假设：亲电子试剂的 N-杂环卡宾 (NHC) 活化可以与后过渡金属（例如 Au、Pd、Ru 和 Ir）同时进行的底物活化合并。我们将利用这一强大的原理来开发许多重要的化学转化。这些例子包括： 1. NHC/过渡金属催化的醛的烯丙基官能化； 2. NHC/Au催化简单烯烃的分子间加氢酰化反应； 3.通过NHC活化和过渡金属催化脱氢/氢转移开发“可编程”安息香缩合反应。在每种情况下，通过正确选择催化剂组分可以实现对化学选择性、区域选择性和对映选择性的精确控制。我们将追求的第二个研究领域是双分子概念，作为改进或新颖的铜催化氧化功能化的策略。我们将开发两种双金属含铜催化剂：一种旨在促进有机金属氧化酶活性，例如允许芳烃和酮的氧化偶联；另一种旨在促进有机金属氧化酶的活性，例如芳烃和酮的氧化偶联。第二个旨在模拟二铜羟基化酶的反应性，以实现选择性 sp3 C-H 键氧化异功能化。我们开发的概念和知识将允许与简单而丰富的底物（例如烯烃、醛、醇和 C-H 键）进行新的反应，所有这些都将对化学合成产生重大影响。