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

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。为了开发新的和有用的反应性，我们已经确定了我们打算重点研究的两个核心领域。一个领域集中在亲电试剂的n -杂环碳（NHC）激活可以与晚期过渡金属（如Au， Pd， Ru和Ir）同时激活底物的假设上。我们将利用这一强有力的原理来发展一些重要的化学转化。这些例子包括：1；NHC/过渡金属催化醛的烯丙基功能化2. NHC/ au催化的简单烯烃分子间氢酰化反应和3。NHC活化和过渡金属催化脱氢/氢转移“可编程”苯甲酸缩合反应的发展。在每种情况下，对化学、区域和对映体选择性的精细控制可以通过适当选择催化剂成分来实现。我们将追求的第二个研究领域是双分子的概念，作为一种策略，以实现改进或新颖的cu催化氧化功能化。我们将开发两个分支的双金属含铜催化剂：一个旨在促进有机金属氧化酶的活性，并允许，例如，芳烃和酮的氧化偶联；第二项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进行新的反应，例如烯烃，醛，醇和C-H键，所有这些都将对化学合成产生重大影响。

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.