Light in Gold Catalysis

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(14), P. 8868 - 8925

Published: Jan. 25, 2021

Within the wide family of gold-catalyzed reactions, gold photocatalysis intrinsically features unique elementary steps. When catalysis meets photocatalysis, a valence change center can easily be achieved via electron transfer and radical addition, avoiding use stoichiometric sacrificial external oxidants. The excellent compatibility radicals with catalysts opens door to series important organic transformations, including redox-neutral C–C C–X coupling, C–H activation, formal radical–radical cross-coupling. complexes nicely complements existing photoredox strategies also new avenue for chemistry. This review covers transformations both mononuclear gold(I) (with without photosensitizer) dinuclear photocatalysts. Various fascinating methodologies, their value chemists, current mechanistic understanding are discussed. most recent examples demonstrate feasibility both, participate in excited state energy (EnT), rather than transfer. rare applications gold(III) photocatalysts, homogeneous heterogeneous, summarized.

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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Oxidant-free oxidative gold catalysis: the new paradigm in cross-coupling reactions

Chemical Communications, Journal Year: 2018, Volume and Issue: 54(79), P. 11069 - 11083

Published: Jan. 1, 2018

The construction of C-C and C-X (X = hetero atom) bonds is the core aspect for assembly molecules. In this regard, late transition-metal-catalyzed cross-coupling reactions have retained their dominance decades. Lately, gold catalysts been emerging as a reliable contender such transformations owing to recent findings that reveal gold's potential beyond carbophilic π-Lewis acid. newfound ability undergo redox under certain circumstances has allowed us explore viable alternative other transition-metals efficient cross-coupled products. This feature article critically presents an overview all neutral enabled by catalysis, which we believe would stimulate further research activities in promising area.

Language: Английский

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Optimization of Catalysts and Conditions in Gold(I) Catalysis—Counterion and Additive Effects

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(14), P. 8452 - 8477

Published: Jan. 21, 2021

Gold catalysis has proven to be an important breakthrough for organic synthesis. The tunable nature of gold catalysts, the unique properties gold, and mild reaction conditions required in many gold-catalyzed reactions have all contributed substantially this metal's popularity catalysis. However, still suffer from limitations such as low turnover numbers (TON). Optimization catalysts may significantly improve efficiency reactions. In review, we will present leading examples counterion or additive-regulated a mechanistic perspective. We pay special attention physical counterion/additive, affinity hydrogen bond basicity, discuss their effects on reactivity catalysts.

Language: Английский

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1,2-Migrations onto Gold Carbene Centers

Chemical Reviews, Journal Year: 2020, Volume and Issue: 121(14), P. 8948 - 8978

Published: Oct. 7, 2020

Gold carbenes are highly active intermediates in homogeneous gold catalysis, enabling a large array of transformations such as C–H/X–H insertions, cyclopropanations, and 1,2-migrations. Unlike insertions 1,2-migrations onto carbene centers seem to be attracting less attention. There has been no comprehensive review focusing on this topic, even though chemistry become powerful tool for the rapid simple construction molecular complexity. This provides critical information centers, drawing preliminary conclusion migratory aptitude various groups. The is divided into several parts according kind precursors.

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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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-Catalyzed Heck Reaction

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(16), P. 8810 - 8816

Published: April 16, 2023

Herein, we report a gold-catalyzed Heck reaction facilitated by the ligand-enabled Au(I)/Au(III) redox catalysis. The elementary organometallic steps such as migratory insertion and β-hydride elimination have been realized in catalytic fashion for first time gold chemistry. present methodology not only overcomes limitations of previously known transition metal-catalyzed reactions requirement specialized substrates formation mixture regioisomeric products result undesirable chain-walking process but also offers complementary regioselectivity compared to other metal

Language: Английский

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DFT-Enabled Development of Hemilabile (P^∧N) Ligands for Gold(I/III) RedOx Catalysis: Application to the Thiotosylation of Aryl Iodides

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(6), P. 3660 - 3674

Published: Feb. 5, 2024

Ligand-enabled oxidative addition of Csp2-X bonds to Au(I) centers has recently appeared as a valuable strategy for the development catalytic RedOx processes. Several cross-coupling reactions that were previously considered difficult achieve reported lately, thus expanding synthetic potential gold(I) complexes beyond traditional nucleophilic functionalization π-systems. MeDalPhos played an important role in this and, despite several studies on alternative structures, remains, so far, only general ligand such process. We report herein discovery and DFT-enabled structural optimization new family hemilabile (P∧N) ligands can promote aryl iodides gold(I). These flexible ligands, which possess common 2-methylamino heteroaromatic N-donor motif, are structurally electronically tunable, being easily accessible affordable. The corresponding shown outperform reactivity (MeDalPhos)Au(I) series alkoxy- amidoarylations alkenes. Their comparatively higher further highlighted thiotosylation iodides, challenging unreported C–S reaction could not be achieved under classical Pd(0/II) catalysis allows divergent access sulfur derivatives.

Language: Английский

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