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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Control of Redox‐Active Ester Reactivity Enables a General Cross‐Electrophile Approach to Access Arylated Strained Rings**

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(33)

Опубликована: Июнь 11, 2022

Strained rings are increasingly important for the design of pharmaceutical candidates, but cross-coupling strained remains challenging. An attractive, underdeveloped, approach to diverse functionalized carbocyclic and heterocyclic frameworks containing all-carbon quaternary centers is coupling abundant strained-ring carboxylic acids with aryl halides. Herein we disclose development a nickel-catalyzed cross-electrophile that couples variety ring N-hydroxyphthalimide (NHP) esters, derived from acid in one step, various heteroaryl halides under reductive conditions. The chemistry enabled by discovery methods control NHP ester reactivity, tuning solvent or using modified

Язык: Английский

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H-Bonded Counterion-Directed Enantioselective Au(I) Catalysis

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(8), С. 3497 - 3509

Опубликована: Фев. 9, 2022

A new strategy for enantioselective transition-metal catalysis is presented, wherein a H-bond donor placed on the ligand of cationic complex allows precise positioning chiral counteranion responsible asymmetric induction. The successful implementation this paradigm demonstrated in 5-exo-dig and 6-endo-dig cyclizations 1,6-enynes, combining an achiral phosphinourea Au(I) chloride with BINOL-derived phosphoramidate Ag(I) salt thus allowing first general use anions Au(I)-catalyzed reactions challenging alkyne substrates. Experiments modified complexes anions, 1H NMR titrations, kinetic data, studies solvent nonlinear effects substantiate key H-bonding interaction at heart catalytic system. This conceptually novel approach, which lies intersection metal catalysis, organocatalysis, counterion-directed provides blueprint development supramolecularly assembled ligands complexes.

Язык: Английский

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Metalloradical Activation of In Situ-Generated α-Alkynyldiazomethanes for Asymmetric Radical Cyclopropanation of Alkenes

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(5), С. 2368 - 2378

Опубликована: Янв. 31, 2022

α-Alkynyldiazomethanes, generated in situ from the corresponding sulfonyl hydrazones presence of a base, can serve as effective metalloradicophiles Co(II)-based metalloradical catalysis (MRC) for asymmetric cyclopropanation alkenes. With D2-symmetric chiral amidoporphyrin 2,6-DiMeO-QingPhyrin optimal supporting ligand, system efficiently activate different α-alkynyldiazomethanes at room temperature highly broad range This catalytic radical process provides general synthetic tool stereoselective construction alkynyl cyclopropanes high yields with both diastereoselectivity and enantioselectivity. Combined computational experimental studies offer several lines evidence support underlying stepwise mechanism Co(II)-catalyzed olefin involving unique α-metalloradical intermediate that is associated two resonance forms α-Co(III)-propargyl γ-Co(III)-allenyl radical. The resulting enantioenriched cyclopropanes, showcased stereospecific transformations, may valuable building blocks organic synthesis.

Язык: Английский

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Recent advances towards organocatalytic enantioselective desymmetrizing reactions

Trends in Chemistry, Год журнала: 2022, Номер 4(3), С. 191 - 205

Опубликована: Янв. 22, 2022

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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Asymmetric gold catalysis enabled by specially designed ligands

Organic Chemistry Frontiers, Год журнала: 2024, Номер 11(6), С. 1858 - 1895

Опубликована: Янв. 1, 2024

This review is planned to provide a comprehensive overview of the progress made in design and development chiral ligands for asymmetric gold catalysis.

Язык: Английский

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