Introduction to Gold Catalysis
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Gold Catalysis sentence examples within Homogeneou Gold Catalysis
Homogeneous gold catalysis has experienced extraordinary development since the dawn of this millennium.
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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.
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Gold Catalysis sentence examples within 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.
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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.
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Gold Catalysis sentence examples within 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.
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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.
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Gold Catalysis sentence examples within Asymmetric Gold Catalysis
The development of sintering resistant gold nanocatalysts is one of the central tasks in gold catalysis.
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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.
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The outlined protocol may serve as a rapid tool to probe the viability of proposed mechanistic pathways in the field of gold catalysis.
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By conceptualizing the idea of "Divergent Gold Catalysis (DGC)", this review aims to consolidate all such reports and provide a unified approach necessary to pave the way for further advancement of this exciting area.
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Homogeneous gold catalysis has experienced extraordinary development since the dawn of this millennium.
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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.
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This chemistry—via cooperative gold catalysis enabled by a chiral bifunctional phosphine ligand—achieves asymmetric catalytic deprotonation of propargylic C–H (pKa > 30) by a tertiary amine group (pKa ≈ 10) of the ligand in the presence of much more acidic aldehydic α-hydrogens (pKa ≈ 17).
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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.
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We report an unprecedented C-H bond functionalization of cyclopropenes enabled by dinuclear gold catalysis.
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3 Gold Catalysis3 Arylation with Directing Group Assistance3.
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The examples summarized herein showcase such possibilities, with special emphasis on tranannular gold catalysis and the emerging ruthenium-catalyzed trans-hydrometalation chemistry for the selective functionalization of alkynes.
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This kinetic barrier is addressed in this study by an efficient piezo-enhanced gold catalysis as demonstrated by the room temperature reduction of dinitrogen into ammonia.
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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.
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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.
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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.
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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.
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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.
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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.
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Here, we demonstrate that homogeneous gold catalysis offers a mild, chemoselective, and practical approach to functionalize high-volume commodity aromatic polymers.
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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.
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Gold catalysis has proven to be an important breakthrough for organic synthesis.
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Here we report the first example of alkyne trifunctionalization through simultaneous construction of C-C, C-O, and C-N bonds via gold catalysis.
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When gold catalysis meets photocatalysis, a valence change of the gold center can easily be achieved via electron transfer and radical addition, avoiding the use of stoichiometric sacrificial external oxidants.
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The reaction of propargyl esters with alkynylsilanes under gold catalysis provides vinylallene derivatives through consecutive [1,2]-acyloxy/[1,2]-silyl rearrangements.
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Asymmetric gold catalysis has been rapidly developed in the past ten years.
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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.
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During an investigation into the potential union of Lewis basic isothiourea organocatalysis and gold catalysis, the formation of gold-isothiourea complexes was observed.
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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.
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Firstly, a general method for the hydroamination of propargylic alcohols with anilines is described using gold catalysis to give 3-hydroxyimines with complete regioselectivity.
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ABSTRACT Gold catalysis in the last two decade has witnessed remarkable improvements in terms of efficiency and scope of application in numerous organic reactions.
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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.
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Gold has been considered an inert metal in catalysis until the seminal work of Teles and Hashmi unveiled the potential of homogeneous gold catalysis.
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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.
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This synthesis features a stereoselective construction of the key 2,5-dihydrofuran ring in the natural product via a recently developed asymmetric gold catalysis.
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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.
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The metal–support interaction plays an important role in gold catalysis.
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An expedient strategy for the synthesis of 5-oxazole ketones was developed via homogeneous gold catalysis with 4-MeO-TEMPO as an oxidant.
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The key elements of the synthesis include a kinetic resolution of racemic 2-silyoxyaldehyde through the allenoate γ-addition to yield the γ-adduct as a single isomer and the subsequent gold catalysis to form the butenolide core.
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Reported herein is the isolation and characterization, for the first time, of a σ-gold allenyl complex as an intermediate in gold catalysis.
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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.
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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.
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, Au xTi yO z q) is an important way to uncover the molecular-level mechanisms of gold catalysis in the related heterogeneous catalytic systems.
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Herein, we demonstrate by means of quantum chemical methods and experiments that the head-to-head dimerization of chloroarylacetylenes can be achieved via mono gold catalysis.
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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.
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Homogeneous gold catalysis is regarded as a landmark addition to the field of organic synthesis.
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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.
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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.
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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.
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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.
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The formal insertion of alkenes into aromatic chloro- and bromoalkynes takes place under cationic gold catalysis.
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Notably, this transformation represents the first use of CF3- and SF5-alkynes in gold catalysis.
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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.
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The development of novel ligands specifically tailored for homogeneous gold catalysis permits the development of new gold catalysis.
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Gold catalysis is a convenient tool to oxidatively functionalize alkyne into a range of valuable compounds.
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Reported here is a strategy based on gold catalysis that is enabled by a designed chiral bifunctional biphenyl-2-ylphosphine ligand.
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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%.
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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.
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An efficient method was developed for the synthesis of substituted aryl-fused pyrazolooxazepines from ortho-O-propargyl aryl pyrazoles by gold catalysis.
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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.
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The synthesis, reactivity, and potential of well-defined dinuclear gold complexes as precursors for dual-gold catalysis is explored.
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