Total Synthesis of Natural Products using Gold Catalysis DOI
Soumik De, Aritra Kumar Dan, Raghaba Sahu

et al.

Chemistry - An Asian Journal, Journal Year: 2022, Volume and Issue: 17(24)

Published: Oct. 18, 2022

Gold catalysis is an extremely enthusiastic field of investigation in the area. The development alternative, highly inventive, precompetitive techniques based on gold has paved way for executing a broad spectrum chemical transformations from uncomplicated starting materials. total synthesis natural products complex and more complicated task. An amalgamation product through gold-catalysis been thought-provoking job. protocol solved several problems related to numerous products. Thus, this review outlined some most notable benchmarks last seven years (2015-2021) their application strategy acquired by authors accomplish will be elaborately discussed emphasizing role gold-catalyzed reactions.

Language: Английский

Divergent Gold Catalysis: Unlocking Molecular Diversity through Catalyst Control DOI
Chetan C. Chintawar, Amit Kumar Yadav, Anil Kumar

et al.

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

Citations

251

The interplay of carbophilic activation and Au(i)/Au(iii) catalysis: an emerging technique for 1,2-difunctionalization of C–C multiple bonds DOI
Vivek W. Bhoyare, Akash G. Tathe, Avishek Das

et al.

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

Citations

150

DFT-Enabled Development of Hemilabile (PN) Ligands for Gold(I/III) RedOx Catalysis: Application to the Thiotosylation of Aryl Iodides DOI

Karim Muratov,

Emil Zaripov, Maxim V. Berezovski

et al.

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

Citations

23

H-Bonded Counterion-Directed Enantioselective Au(I) Catalysis DOI Creative Commons
Allegra Franchino, Àlex Martí, Antonio M. Echavarren

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(8), P. 3497 - 3509

Published: Feb. 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.

Language: Английский

Citations

56

Control of Redox‐Active Ester Reactivity Enables a General Cross‐Electrophile Approach to Access Arylated Strained Rings** DOI
Daniel C. Salgueiro, K. Benjamin, Ilia A. Guzei

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(33)

Published: June 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

Language: Английский

Citations

56

Metalloradical Activation of In Situ-Generated α-Alkynyldiazomethanes for Asymmetric Radical Cyclopropanation of Alkenes DOI
Jing Ke, Wan‐Chen Cindy Lee, Xiaoxu Wang

et al.

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(5), P. 2368 - 2378

Published: Jan. 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.

Language: Английский

Citations

53

Recent advances towards organocatalytic enantioselective desymmetrizing reactions DOI
Yin Xu,

Tong‐Yi Zhai,

Zhou Xu

et al.

Trends in Chemistry, Journal Year: 2022, Volume and Issue: 4(3), P. 191 - 205

Published: Jan. 22, 2022

Language: Английский

Citations

48

Enantioselective C−H Functionalization Reactions under Gold Catalysis DOI
Avishek Das, Nitin T. Patil

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(20)

Published: Jan. 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.

Language: Английский

Citations

43

L‐Shaped Heterobidentate Imidazo[1,5‐a]pyridin‐3‐ylidene (N,C)‐Ligands for Oxidant‐Free AuI/AuIII Catalysis DOI
Pengcheng Gao, Jihong Xu, Tongliang Zhou

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(12)

Published: Jan. 25, 2023

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

Language: Английский

Citations

40

Asymmetric gold catalysis enabled by specially designed ligands DOI
Amol B. Gade,

Urvashi Urvashi,

Nitin T. Patil

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(6), P. 1858 - 1895

Published: Jan. 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.

Language: Английский

Citations

13