Divergent Gold Catalysis: Unlocking Molecular Diversity through Catalyst Control

Chemical Reviews, Год журнала: 2021, Номер 121(14), С. 8478 - 8558

Опубликована: Фев. 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.

Язык: 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, Год журнала: 2021, Номер 50(18), С. 10422 - 10450

Опубликована: Янв. 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.

Язык: 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, Год журнала: 2024, Номер 146(6), С. 3660 - 3674

Опубликована: Фев. 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.

Язык: Английский

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Copper‐Catalyzed Asymmetric Diyne Cyclization via [1,2]‐Stevens‐Type Rearrangement for the Synthesis of Chiral Chromeno[3,4‐c]pyrroles

Angewandte Chemie International Edition, Год журнала: 2021, Номер 61(7)

Опубликована: Дек. 14, 2021

Here, we report a copper-catalyzed asymmetric cascade cyclization/[1,2]-Stevens-type rearrangement via non-diazo approach, leading to the practical and atom-economic assembly of various valuable chiral chromeno[3,4-c]pyrroles bearing quaternary carbon stereocenter in generally moderate good yields with wide substrate scope excellent enantioselectivities (up 99 % ee). Importantly, this protocol not only represents first example catalytic [1,2]-Stevens-type based on alkynes but also constitutes formal carbene insertion into Si-O bond.

Язык: Английский

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Enantioselective C−H Functionalization Reactions under Gold Catalysis

Chemistry - A European Journal, Год журнала: 2022, Номер 28(20)

Опубликована: Янв. 11, 2022

Abstract Transition metal‐catalyzed enantioselective functionalization of ubiquitous C−H bonds has proven to be promising field as it offers the construction chiral molecular complexity in a step‐ and atom‐economical manner. In recent years, gold emerged an attractive contender for catalyzing such reactions. The unique reactivities selectivities offered by catalysts have been exploited access numerous asymmetric transformations based on gold‐catalyzed processes. Herein, this review critically highlights major advances discoveries made under catalysis which is accompanied mechanistic insights at appropriate places.

Язык: Английский

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L‐Shaped Heterobidentate Imidazo[1,5‐a]pyridin‐3‐ylidene (N,C)‐Ligands for Oxidant‐Free Au^I/Au^III Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(12)

Опубликована: Янв. 25, 2023

In the last decade, major advances have been made in homogeneous gold catalysis. However, Au

Язык: Английский

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Catalytic Asymmetric Deoxygenative Cyclopropanation Reactions by a Chiral Salen-Mo Catalyst

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(5), С. 2765 - 2772

Опубликована: Янв. 10, 2023

The catalytic asymmetric cyclopropanation reaction of alkenes with diazo compounds is a direct and powerful method to construct chiral cyclopropanes that are essential drug discovery. However, potentially explosive often require hazardous reagents for their preparation. Here, we report on the use 1,2-dicarbonyl as safe readily available surrogates in deoxygenative reaction. Enabled by class simple accessible salen-Mo catalysts, proceeded generally good enantioselectivities yields toward wide range substrates (80 examples). Preliminary mechanistic studies suggested proposed μ-oxo bridged dinuclear Mo(III)-species was catalytically active species. This strategy not only provides promising route synthesis but also opens new window potential applications complexes catalysis.

Язык: Английский

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Recent Advances in the Gold-Catalyzed Reactions of Propargyl Esters

Accounts of Chemical Research, Год журнала: 2023, Номер 56(12), С. 1406 - 1420

Опубликована: Июнь 6, 2023

ConspectusLate-transition-metal-based complexes represent an indispensable catalytic tool in chemical synthesis due to their ability increase molecular complexity rapidly and efficiently from readily accessible substrates a single operation. Added this is the exquisite control of product chemo-, diastereo-, enantio-, site-selectivities achieved by systems transition-metal salts that have been developed mediate wide range functional group transformations. Within venerable synthetic toolbox, Au(I) Au(III) emerged recent years as invaluable addition result potent σ- π-Lewis acidities stabilize cationic reaction intermediates. The insights provided mechanistic studies examining various electronic, steric, stereoelectronic factors at play organogold species are expected be formed chemistry complex also pivotal understanding exploring potential utility. Illustrative this, for example, contribution made gold-catalyzed cycloisomerization propargyl esters strategies variety bioactive natural products compounds current pharmaceutical materials interest. This Account summarizes our efforts over past decade toward realizing new single-step carbocyclic heterocyclic relied on reactions esters. It outlines methods exploited unique reactivities gold-carbene typically generated [2,3]-sigmatropic rearrangement compound class containing terminal or electron-deficient alkyne moiety exposure salt. describes realization initiated 1,3-acyloxy migration with electronically unbiased disubstituted C≡C bond delivers corresponding allenyl ester primed further reactivity activation 11 metal complex. part ongoing overarching program within was focused determining gold catalysis would enable application recognizable disconnections retrosynthetic analysis. They were additionally aimed evaluating opportunities offered relativistic effects possessed complex, most pronounced among d-block elements thus catalyst choice chemistry, generate space. For instance, we demonstrated several 1,3- 1,4-enyne reliable strategy situ formation 1,4-cyclopentadienyl derivatives. Their appropriately placed second starting material then shown afford targets five-membered ring structure. An example assembly member 1H-isoindole family found exhibit TNF-α (tumor necrosis factor-α) inhibitor activity.

Язык: Английский

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Enantioselective Construction of Quaternary Stereocenters via A Chiral Spiro Phosphoric Acid-Assisted Formal Gold Carbene gem-Dialkylation Reaction

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(28), С. 19261 - 19270

Опубликована: Июль 1, 2024

Enantioselective construction of all-carbon quaternary stereocenters has attracted much attention over the past few decades. A variety catalytic asymmetric methods have been disclosed based on use presynthesized complex reagents that impart congested steric hindrance to reaction center, which generally produce chiral molecules through forming one C-C bond. The readily available could build two bonds same carbonic center with concomitant assembly remains challenging. Herein, we disclose a alkyne multifunctionalization using gold and spiro phosphoric acid (SPA) for synergistic catalysis. In this method, accessible internal alkynes served as key carbene precursors, followed by

Язык: Английский

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Dirhodium-Catalyzed Asymmetric Transformations of Alkynes via Carbene Intermediates

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Янв. 31, 2025

ConspectusFunctionalization of alkynes is an established cornerstone organic synthesis. While numerous transition metals exhibit promising activities in the transformations via π-insertion or oxidative cyclometalation, Lewis π-acids offer a different approach. By coordinating with through π-bonding, facilitate nucleophilic addition, leading to formation alkenyl metal species. These species can undergo electron rearrangement generate carbenes, which are crucial intermediates for subsequent carbene transfer reactions. This reaction pathway provides versatile route alkyne functionalization, especially asymmetric manner. Although π-acid, gold(I), pioneered this mode, development variants remains challenging due linear coordination gold(I). Therefore, expanding range catalysts beyond gold(I) complexes other would further advances chiral molecule construction and exploration novel modes.In Account, we present concise review multifunctionalization dirhodium-catalyzed transformations, providing modulation strategies substrates plausible mechanisms. In aromatization-driven strategy, furanyl dirhodium generated from enynone, terminated by enantioselective intramolecular C-H insertion, cyclopropanation, aromatic substitution, Büchner reaction, giving dihydroindoles, dihydrobenzofurans, cyclopropane-fused tetrahydroquinolines, fluorenes, cyclohepta[b]benzofurans. The cap-tether strategy was developed study balance reactivity selectivity azo-enyne. gave first catalytic cycloisomerization azo-enyne, affording centrally axially isoindazole derivatives. synergistic activation i.e., EWG C-H···O interaction, introduced achieve enynes, cyclopropane-annulated bicyclic systems enynals. Benefiting these successes, difluoromethyl-substituted enynes were designed proven be effective substrates. With corresponding benzo-1,6-enynes as substrates, biscyclopropanation cascaded cyclopropanation/cyclopropenation achieved using dicarbene equivalents. Additionally, benzo-1,5-enynal vinyl carbene, reacted variety alkenes [2 + 1] cycloaddition, [4 3] formal allylation, spiro fused polycyclic heterocycles. Coupling desymmetrization, successfully diynals, constructing furan-fused dihydropiperidines alkyne-substituted aza-quaternary stereocenter. Notably, analyzing X-ray structures several dirhodium-alkyne π-complexes, together results DFT calculations control experiments, obtained evidence supporting making well-defined paddlewheel-like dirhodium(II) stand out among complexes. We anticipate that our research will significantly advance fields dirhodium, alkyne, chemistry.

Язык: Английский

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