Cyclic (Alkyl)- and (Aryl)-(amino)carbene Coinage Metal Complexes and Their Applications

Chemical Reviews, Journal Year: 2020, Volume and Issue: 120(9), P. 4141 - 4168

Published: April 2, 2020

Cyclic (alkyl)- and (aryl)-(amino)carbenes (CAACs CAArCs) are stronger σ-donors π-acceptors than imidazol-2-ylidenes imidazolidin-2-ylidenes, the well-known N-heterocyclic carbenes (NHCs). Consequently, they form strong bonds with coinage metals stabilize both low high oxidation states. This Review shows that CAACs CAArCs have allowed for isolation of copper gold complexes were believed to be only transient intermediates. has not a better understanding mechanism known processes but also led development novel metal-catalyzed reactions. In addition their role in homogeneous catalysis, CAAC CAArC metal recently found applications medicinal chemistry, as well materials science. When possible, performance ligands compared those classical NHCs.

Language: Английский

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Divergent Gold Catalysis: Unlocking Molecular Diversity through Catalyst Control

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(14), P. 8478 - 8558

Published: Feb. 8, 2021

The catalyst-directed divergent synthesis, commonly termed as "divergent catalysis", has emerged a promising technique it allows chartering of structurally distinct products from common substrates simply by modulating the catalyst system. In this regard, gold complexes powerful catalysts they offer unique reactivity profiles compared to various other transition metal catalysts, primarily due their salient electronic and geometrical features. Owing tunable soft π-acidic nature, not only evolved superior contenders for catalyzing reactions alkynes, alkenes, allenes but also, more intriguingly, have been found provide reaction pathways over π-acid such Ag, Pt, Pd, Rh, Cu, In, Sc, Hg, Zn, etc. recent past witnessed renaissance in examples wherein, choosing or fine-tuning ligands, counteranions oxidation states itself, complete switch was observed. However, reviews documenting are sporadic; result, most reports kind remained scattered literature, thereby hampering further development burgeoning field. By conceptualizing idea "Divergent Gold Catalysis (DGC)", review aims consolidate all unified approach necessary pave way advancement exciting area. Based on factors governing divergence product formation, an explicit classification DGC provided. To gain fundamental understanding observed reactivities selectivities, is accompanied mechanistic insights at appropriate places.

Language: Английский

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Recent Advances in Gold(III) Chemistry: Structure, Bonding, Reactivity, and Role in Homogeneous Catalysis

Chemical Reviews, Journal Year: 2020, Volume and Issue: 121(14), P. 8364 - 8451

Published: Sept. 23, 2020

Over the past decade organometallic chemistry of gold(III) has seen remarkable advances. This includes synthesis first examples several compound classes that have long been hypothesized as being part catalytic cycles, such alkene, alkyne, CO and hydride complexes, important catalysis-relevant reaction steps at last demonstrated for gold, like migratory insertion β-H elimination reactions. Also, pathways were already known, example generation intermediates by oxidative addition their reductive elimination, are much better understood. A deeper understanding fundamental reactivity revealed unexpected mechanistic avenues, which can open when barriers reactions other metals would be regarded "standard" too high. review summarizes evaluates these developments, together with applications in catalysis, emphasis on insight gained investigations.

Language: Английский

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Homogeneous Gold Redox Chemistry: Organometallics, Catalysis, and Beyond

Trends in Chemistry, Journal Year: 2020, Volume and Issue: 2(8), P. 707 - 720

Published: June 2, 2020

Language: Английский

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Gold‐Catalyzed Cross‐Coupling Reactions: An Overview of Design Strategies, Mechanistic Studies, and Applications

Chemistry - A European Journal, Journal Year: 2019, Volume and Issue: 26(7), P. 1442 - 1487

Published: Oct. 28, 2019

Abstract Transition‐metal‐catalyzed cross‐coupling reactions are central to many organic synthesis methodologies. Traditionally, Pd, Ni, Cu, and Fe catalysts used promote these reactions. Recently, studies have showed that both homogeneous heterogeneous Au can be for activating selective Here, an overview of the past studies, current trends, future directions in field gold‐catalyzed coupling is presented. Design strategies accomplish homocoupling under conditions, computational experimental mechanistic their applications diverse fields critically reviewed. Specific topics covered are: oxidant‐assisted oxidant‐free reactions; strain‐assisted dual photoredox catalysis; bimetallic synergistic mechanisms reductive elimination processes; enzyme‐mimicking chemistry; cluster surface plasmonic catalysis. In relevant sections, theoretical I /Au III chemistry discussed predictions from calculations compared with observations derive useful design strategies.

Language: Английский

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The interplay of carbophilic activation and Au(i)/Au(iii) catalysis: an emerging technique for 1,2-difunctionalization of C–C multiple bonds

Chemical Society Reviews, Journal Year: 2021, Volume and Issue: 50(18), P. 10422 - 10450

Published: Jan. 1, 2021

This review highlights a decade-long journey of Au-catalyzed 1,2-difunctionalization reactions C–C multiple bonds that have been realized due to the productive integration Au( i )/Au( iii )catalysis with unique π-activation mode gold complexes.

Language: Английский

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Main Avenues in Gold Coordination Chemistry

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(14), P. 8311 - 8363

Published: Feb. 9, 2021

In this contribution, we provide an overview of the main avenues that have emerged in gold coordination chemistry during last years. The unique properties motivated research chemistry, and especially regarding applications compounds catalysis, medicine, materials chemistry. advances synthesis knowledge been possible with design novel ligands becoming relevant motifs allowed preparation elusive complexes area research. Strong donor easily modulable electronic steric properties, such as stable singlet carbenes or cyclometalated ligands, decisive stabilization gold(0) species, fluoride complexes, hydrides, unprecedented π cluster derivatives. These new important not only from fundamental structure bonding studies but also for sophisticated catalysts to improve activity selectivity organic transformations. Moreover, they enabled facile oxidative addition gold(I) gold(III) a plethora specific properties.

Language: Английский

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Recent Advances in Metal‐Catalyzed Functionalization of Indoles

Advanced Synthesis & Catalysis, Journal Year: 2021, Volume and Issue: 363(11), P. 2723 - 2739

Published: April 7, 2021

Abstract Indole is one of the most important heterocycles in organic synthesis, natural products, and drug discovery. Recently, tremendous advances selective functionalization indoles have been reported. Although powered by transition metal catalysis, exceedingly useful methods absence metals also In this review, we provide an overview reactions that published last years with a focus on recent advances, aims, future trends. The review organized positional selectivity type used for functionalization. particular, discuss major transition‐metal‐catalyzed C−H at classical C2/C3 positions, remote C4/C7 cross‐coupling, transition‐metal‐free magnified image

Language: Английский

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Enantioselective Au(I)/Au(III) Redox Catalysis Enabled by Chiral (P,N)-Ligands

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(16), P. 7089 - 7095

Published: April 18, 2022

Presented herein is the first report of enantioselective Au(I)/Au(III) redox catalysis, enabled by a newly designed hemilabile chiral (P,N)-ligand (ChetPhos). The potential this concept has been demonstrated development 1,2-oxyarylation and 1,2-aminoarylation alkenes which provided direct access to medicinally relevant 3-oxy- 3-aminochromans (up 88% yield 99% ee). DFT studies were carried out unravel enantiodetermining step, revealed that stronger trans influence phosphorus allows selective positioning substrate in C2-symmetric environment present around nitrogen, imparting high level enantioselectivity.

Language: Английский

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Gold (I/III)‐Catalyzed Trifluoromethylthiolation and Trifluoromethylselenolation of Organohalides

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(12)

Published: Jan. 21, 2022

Abstract The first C−SCF 3 /SeCF cross‐coupling reactions using gold redox catalysis [(MeDalphos)AuCl], AgSCF or Me 4 NSeCF , and organohalides as substrates are reported. new methodology enables a one‐stop shop synthesis of aryl/alkenyl/alkynyl trifluoromethylthio‐ selenoethers with broad substrate scope (>60 examples up to 97 % isolated yield). method is scalable, its robustness evidenced by the late‐stage functionalization various bioactive molecules, which makes this reaction an attractive alternative in for pharmaceutical agrochemical research development.

Language: Английский

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