Gold Catalysis(金催化)研究综述
Gold Catalysis 金催化 - The development of sintering resistant gold nanocatalysts is one of the central tasks in gold catalysis. [1] Now protein evolution has enabled the control of selectivity for hydroamination reactions catalysed by gold-based artificial metalloenzymes by favouring dual-gold catalysis over monomeric catalysis. [2] The outlined protocol may serve as a rapid tool to probe the viability of proposed mechanistic pathways in the field of gold catalysis. [3] The dramatically enhanced ECL emission of self-assembled AuAg NCs originates from the synergistic effect of aggregation-induced enhancement and silver effect in gold catalysis. [4] By introducing various stimuli into the transmission electron microscope (TEM) sample chamber, in-situ TEM has enabled researchers to carry out experiments directly in the TEM, leading to extensive discoveries on the atomic-scale dynamic processes of materials and crucial mechanistic insights on the origin of material’s behaviors such as size-effect in gold catalysis, toughening mechanism of high entropy alloys, and degradation mechanisms of battery materials. [5] The inherently strained furan-fused cyclobutenes, in situ generated via cycloisomerizations of allenyl ketones bearing cyclopropyl moiety under gold catalysis, have been utilized as reactive building blocks toward cross cycloadditions. [6] The ynamides reactivity towards nitrogen-transfer reagents, such as azides, nitrogen ylides, isoxazoles, and anthranils; oxygen atom-transfer reagents, like nitrones, sulfoxides, and pyridine N-oxides; and carbon nucleophiles under gold catalysis are herein uncovered. [7] The interplay of the two important reactivity modes encountered in gold catalysis, namely carbophilic activation and Au(i)/Au(iii) catalysis, has allowed the development of a novel mechanistic paradigm that sponsors 1,2-difunctionalization reactions of various C-C multiple bonds. [8] The implementation of gold catalysis into large-scale processes suffers from the fact that most reactions still require high catalyst loadings to achieve efficient catalysis thus making upscaling impractical. [9] Gold catalysis has proven to be an important breakthrough for organic synthesis. [10] The application of these axially chiral ImPy-based AuCl complexes in a series of gold catalysis is explored, and varying degrees of asymmetric induction are observed. [11] During an investigation into the potential union of Lewis basic isothiourea organocatalysis and gold catalysis, the formation of gold-isothiourea complexes was observed. [12] Firstly, a general method for the hydroamination of propargylic alcohols with anilines is described using gold catalysis to give 3-hydroxyimines with complete regioselectivity. [13] The focus of this chapter is to provide comprehensive depth of oxidative addition, transmetalation, reductive elimination, β-hydride elimination, and migratory insertion reactions for the benefit of gold catalysis. [14] The cis-difunctionalized product can be obtained by the TMS-substituted alkyne through the gold catalysis, or by the Ph-substituted alkyne through the rhodium catalysis. [15] The metal–support interaction plays an important role in gold catalysis. [16] Reported herein is the isolation and characterization, for the first time, of a σ-gold allenyl complex as an intermediate in gold catalysis. [17] 1,3-Azaprotio transfer of propargylic α-ketocarboxylate oximes, a new type of alkynyl oximes featuring an ester tether, has been explored by taking advantage of gold catalysis. [18] , Au xTi yO z q) is an important way to uncover the molecular-level mechanisms of gold catalysis in the related heterogeneous catalytic systems. [19] High activity, regio-, chemo-, and stereoselectivities are obtained for hydroelementation and domino processes, underlining the excellent performance (TONs and TOFs) of these IPy-based ligands in gold catalysis. [20] Although N-oxides are often considered as oxygen transfer reagents in gold catalysis, benzofurazan N-oxide was found to act as a facile precursor for an α-imino gold carbene intermediate. [21] Although organogermanium compounds are generally believed to be of low reactivity in homogenous catalysis, this report discloses the highly efficient and orthogonal reactivity of aryl germanes with arenes under gold catalysis. [22] Notably, this transformation represents the first use of CF3- and SF5-alkynes in gold catalysis. [23] The chemoselectivity of CH functionalization against over‐oxidation in Zn catalysis, in comparison with gold catalysis, can be jointly controlled by four factors: (1) the use of less nucleophilic N‐oxide, (2) the enhanced electrophilicity and carbocationic nature of the carbenic site in the α‐oxo metal carbenoid intermediate, (3) enhanced steric repulsion to incoming oxidant exerted by bulky ancillary ligand in the close nearby of the carbenic site to disfavor intermolecular over‐oxidation and (4) the large negative value of activation entropy in the intermolecular over‐oxidation pathway, that jointly give rise to lower activation free energy for the intramolecular cyclization/CH functionalization pathway than for the intermolecular over‐oxidation pathway. [24] Gold catalysis is a convenient tool to oxidatively functionalize alkyne into a range of valuable compounds. [25] Reported here is a strategy based on gold catalysis that is enabled by a designed chiral bifunctional biphenyl-2-ylphosphine ligand. [26] The gold catalysis is enabled by a bifunctional phosphine ligand featuring a critical remote tertiary amino group, and the reaction tolerates a range of substituents and exhibits yields up to 96%. [27] Gold catalysis has experienced a tremendous development over the past decades, and is nowadays widely used in organic synthesis to perform chemical transformations of π‐bond‐containing molecules. [28] An efficient method was developed for the synthesis of substituted aryl-fused pyrazolooxazepines from ortho-O-propargyl aryl pyrazoles by gold catalysis. [29] In addition, this is the first example of the generation of an indole/thiophene/pyrrole/pyridine/naphthalene/benzene-fused N-heterocycle library through gold catalysis in water from readily available materials. [30] The synthesis, reactivity, and potential of well-defined dinuclear gold complexes as precursors for dual-gold catalysis is explored. [31]开发耐烧结金纳米催化剂是金催化的核心任务之一。 [1] 现在，蛋白质进化通过支持双金催化而不是单体催化，能够控制由金基人造金属酶催化的加氢胺化反应的选择性。 [2] 概述的协议可以作为一种快速工具来探测金催化领域所提出的机械途径的可行性。 [3] 自组装 AuAg NCs 显着增强的 ECL 发射源于金催化中聚集诱导增强和银效应的协同作用。 [4] 通过在透射电子显微镜 (TEM) 样品室中引入各种刺激，原位 TEM 使研究人员能够直接在 TEM 中进行实验，从而对材料的原子尺度动态过程产生了广泛的发现，并在金催化中的尺寸效应、高熵合金的增韧机制和电池材料的降解机制等材料行为的起源。 [5] 在金催化下通过带有环丙基部分的烯基酮的环异构化原位产生的固有应变呋喃稠合环丁烯已被用作交叉环加成的反应性构件。 [6] ynamides 对氮转移试剂的反应性，例如叠氮化物、氮叶立德、异恶唑和邻氨基苯甲酸；氧原子转移试剂，如硝酮、亚砜和吡啶 N-氧化物；在金催化下的碳亲核试剂和碳亲核试剂在此被揭示。 [7] 金催化中遇到的两种重要反应模式的相互作用，即carbophilic 活化和Au(i)/Au(iii) 催化，已经允许开发一种新的机制范式，该范式赞助了各种C-C 多键的1,2-双官能化反应. [8] 金催化在大规模工艺中的应用受到以下事实的影响：大多数反应仍然需要高催化剂负载量才能实现高效催化，因此扩大规模是不切实际的。 [9] 金催化已被证明是有机合成的重要突破。 [10] 探索了这些轴向手性 ImPy 基 AuCl 配合物在一系列金催化中的应用，并观察到不同程度的不对称诱导。 [11] 在研究路易斯碱性异硫脲有机催化和金催化的潜在结合过程中，观察到金-异硫脲配合物的形成。 [12] 首先，描述了使用金催化将炔丙醇与苯胺加氢胺化的一般方法，以得到具有完全区域选择性的 3-羟基亚胺。 [13] 本章的重点是全面深入地介绍氧化加成、金属转移、还原消除、β-氢化物消除和迁移插入反应，以促进金催化。 [14] 顺式双官能化产物可由TMS取代的炔烃通过金催化得到，或由Ph取代的炔烃通过铑催化得到。 [15] 金属-载体相互作用在金催化中起重要作用。 [16] 本文首次报道了作为金催化中间体的 σ-金烯基配合物的分离和表征。 [17] 已经利用金催化探索了炔丙基α-酮羧酸酯肟的1,3-氮杂丙醇转移，这是一种具有酯系链的新型炔基肟。 [18] , Au xTi yO z q) 是揭示相关多相催化体系中金催化分子水平机制的重要途径。 [19] 对于加氢元素化和多米诺过程，获得了高活性、区域选择性、化学选择性和立体选择性，突显了这些基于 IPy 的配体在金催化中的优异性能（TON 和 TOF）。 [20] 尽管 N-氧化物通常被认为是金催化中的氧转移试剂，但发现苯并呋喃 N-氧化物可作为 α-亚氨基金卡宾中间体的简便前体。 [21] 尽管通常认为有机锗化合物在均相催化中具有低反应性，但本报告揭示了芳基锗烷与芳烃在金催化下的高效和正交反应性。 [22] 值得注意的是，这种转变代表了 CF3-和 SF5-炔烃在金催化中的首次使用。 [23] 与金催化相比，Zn 催化中 CH 功能化对过氧化的化学选择性可以由四个因素共同控制：（1）使用较少亲核的 N-氧化物，（2）增强的亲电性和碳阳离子性质α-氧代金属类卡宾中间体中的卡宾位点，（3）增强了对进入氧化剂的空间排斥，由靠近卡宾位点的庞大辅助配体施加，不利于分子间过氧化和（4）大的负值分子间过氧化途径中的活化熵，共同导致分子内环化/CH功能化途径的活化自由能低于分子间过氧化途径。 [24] 金催化是将炔烃氧化功能化为一系列有价值的化合物的便捷工具。 [25] 这里报道了一种基于金催化的策略，该策略由设计的手性双功能联苯-2-基膦配体实现。 [26] 金催化是由具有关键远程叔氨基的双功能膦配体实现的，该反应耐受一系列取代基，产率高达 96%。 [27] 金催化在过去的几十年中经历了巨大的发展，如今广泛应用于有机合成中，对含 π 键的分子进行化学转化。 [28] 开发了一种通过金催化从邻-O-炔丙基芳基吡唑合成取代芳基稠合吡唑并氧杂氮杂卓的有效方法。 [29] 此外，这是第一个通过金催化在水中从现成的材料中生成吲哚/噻吩/吡咯/吡啶/萘/苯稠合的 N-杂环库的例子。 [30] 探索了定义明确的双核金配合物作为双金催化前体的合成、反应性和潜力。 [31]
Homogeneou Gold Catalysis 均质金催化
Homogeneous gold catalysis has experienced extraordinary development since the dawn of this millennium. [1] Since the beginning of the 2000's homogeneous gold catalysis has emerged as a powerful tool to promote the cyclization of unsaturated substrates with excellent regioselectivity allowing for the synthesis of elaborated organic scaffolds. [2] Here, we demonstrate that homogeneous gold catalysis offers a mild, chemoselective, and practical approach to functionalize high-volume commodity aromatic polymers. [3] During the last two decades, a wide range of distinct synthetic methodologies have been unveiled employing homogeneous gold catalysis and aptly applied in the synthesis of numerous natural products and biologically active molecules. [4] Gold has been considered an inert metal in catalysis until the seminal work of Teles and Hashmi unveiled the potential of homogeneous gold catalysis. [5] An expedient strategy for the synthesis of 5-oxazole ketones was developed via homogeneous gold catalysis with 4-MeO-TEMPO as an oxidant. [6] Homogeneous gold catalysis is regarded as a landmark addition to the field of organic synthesis. [7] The development of novel ligands specifically tailored for homogeneous gold catalysis permits the development of new gold catalysis. [8]自本世纪初以来，均相金催化经历了非凡的发展。 [1] 自 2000 年初以来，均相金催化已成为促进不饱和底物环化的有力工具，具有出色的区域选择性，可用于合成精细的有机支架。 [2] 在这里，我们证明均相金催化提供了一种温和、化学选择性和实用的方法来功能化大批量商品芳烃聚合物。 [3] 在过去的二十年中，使用均相金催化的各种不同的合成方法被揭开，并恰当地应用于许多天然产物和生物活性分子的合成。 [4] 在 Teles 和 Hashmi 的开创性工作揭示了均相金催化的潜力之前，金一直被认为是催化中的惰性金属。 [5] 通过均相金催化，以 4-MeO-TEMPO 作为氧化剂，开发了一种合成 5-恶唑酮的便捷策略。 [6] 均相金催化被认为是有机合成领域的一个里程碑式的补充。 [7] 专门为均相金催化定制的新型配体的开发允许开发新的金催化。 [8]
Related Gold Catalysis
Moreover, mechanistic studies revealed that the generation of donor/donor copper carbenes is presumably involved in this 1,5-diyne cyclization, which is distinctively different from the related gold catalysis, and thus it constitutes a novel way for the generation of donor/donor metal carbenes. [1] In addition, an unexpected [1,3] O-to-C rearrangement is observed in the case of the ynamide substrate bearing a phenyl-substituted alkene, which is distinctively different from the related gold catalysis. [2] Moreover, the mechanistic rationale for this novel cascade cyclization is also strongly supported by control experiments, and is distinctively different from the related gold catalysis. [3]此外，机理研究表明，供体/供体铜卡宾的产生可能参与了这种1,5-二炔环化反应，这与相关的金催化明显不同，因此它构成了一种产生供体/供体的新方法。金属卡宾。 [1] 此外，在带有苯基取代烯烃的炔酰胺底物的情况下，观察到了意想不到的[1,3] O-to-C重排，这与相关的金催化明显不同。 [2] 此外，这种新型级联环化的机理原理也得到了对照实验的大力支持，并且与相关的金催化明显不同。 [3]
Dual Gold Catalysis
A dual gold catalysis mechanism was postulated for transformations involving the formation of C-C bonds by reaction between a terminal alkyne and an enynamide fragment. [1] These species, which can principally be accessed by a 1,2-migration process from a gold-activated alkyne or by dual gold catalysis on a diyne substrate, can react with nucleophilic partners or by C–H insertion to produce a variety of functionalized (poly)cyclic compounds. [2] We postulate a mechanism of dual gold catalysis involving initial formation of gold-π-alkynylgold species that activates a 1,5-hydrogen shift to form reactive 1,6-dipoles, thus furnishing intramolecular Michael-type reactions with nitrosonium electrophiles. [3]假定双金催化机制涉及通过末端炔烃和烯酰胺片段之间的反应形成C-C键的转化。 [1] 这些物质主要可以通过金活化炔烃的 1,2-迁移过程或通过二炔底物上的双金催化获得，可以与亲核伙伴反应或通过 C-H 插入产生各种官能化的（多）环化合物。 [2] 我们假设双金催化机制涉及金-π-炔基金物种的初始形成，该物种激活1,5-氢位移以形成反应性1,6-偶极子，从而提供与亚硝基亲电子试剂的分子内迈克尔型反应。 [3]
Asymmetric Gold Catalysis
Asymmetric gold catalysis has been rapidly developed in the past ten years. [1] This synthesis features a stereoselective construction of the key 2,5-dihydrofuran ring in the natural product via a recently developed asymmetric gold catalysis. [2]不对称金催化在过去十年中得到了快速发展。 [1] 该合成的特点是通过最近开发的不对称金催化在天然产物中立体选择性地构建关键的 2,5-二氢呋喃环。 [2]