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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Hydroelementation of diynes

Chemical Society Reviews, Год журнала: 2022, Номер 51(3), С. 869 - 994

Опубликована: Янв. 1, 2022

This review highlights the hydroelementation reactions of conjugated and separated diynes, which depending on process conditions, catalytic system, as well type reagents, leads to formation various products: enynes, dienes, allenes, polymers, or cyclic compounds. The presence two triple bonds in diyne structure makes these compounds important reagents but selective product is often difficult owing problems associated with maintaining appropriate reaction regio- stereoselectivity. Herein we this topic gain knowledge reactivity diynes systematise range information relating their use reactions. divided according addition E-H (E = Mg, B, Al, Si, Ge, Sn, N, P, O, S, Se, Te) bond bond(s) diyne, reagent used, formed. Not only are comprehensively discussed, synthetic potential obtained products also presented. majority published research included within review, illustrating limitations processes, intent showcase power transformations synthesis materials chemistry.

Язык: Английский

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Hydration reactions catalyzed by transition metal–NHC (NHC = N-heterocyclic carbene) complexes

Coordination Chemistry Reviews, Год журнала: 2023, Номер 485, С. 215110 - 215110

Опубликована: Март 30, 2023

Язык: Английский

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Cyclization Reactions of In Situ-Generated Acyl Ketene with Ynones to Form Oxacycles

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(7), С. 4496 - 4502

Опубликована: Март 20, 2024

Acyl ketenes react with polar unsaturated functional groups to give unique heterocyclic rings, yet reactions unpolarized have not been reported. Herein, we describe two effective ring-forming between acetyl ketene and electron-deficient alkynes. The first reaction involves in situ tethering nucleophile-containing 1,3-diynones, which promotes sequential intramolecular 1,6/1,4-additions generate 2-methylene-2H-pyrans various yields (24–91%). other a zwitterionic intermediate generated from DABCO, undergoes Michael addition terminal alkynyl ketones 3-acyl-4-pyrones (11–79%).

Язык: Английский

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Metal Nanoparticle‐Catalyzed Alkyne Cyclization for the Synthesis of Heterocycles

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(14), С. 3085 - 3104

Опубликована: Май 22, 2024

Abstract Heterocycles are important compounds existed in diverse advanced chemicals, functional materials, bioactive molecules and natural products. Different strategies through transition metal‐catalyzed alkyne cyclization have been developed to synthesize various heterocycles. The merger of metal nanoparticle catalysis has emerged as an approach By using different kinds catalysts, such gold, silver, copper palladium nanoparticles, a number heterocycles prepared with high yield selectivity green, sustainable highly efficient manner. This review summarizes discusses recent achievements nanoparticle‐catalyzed for the synthesis

Язык: Английский

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Synthesis of γ-Pyrones and N-Methyl-4-pyridones via the Au Nanoparticle-Catalyzed Cyclization of Skipped Diynones in the Presence of Water or Aqueous Methylamine

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(13), С. 8525 - 8533

Опубликована: Июнь 9, 2022

Supported Au nanoparticles on TiO2 catalyze the hydration/6-endo cyclization of skipped diynones to γ-pyrones in aqueous dioxane, via triple bond activation. The isomeric 3(2H)-furanones which could be formed through a competing and often prevailing 5-exo pathway using homogeneous ionic Au(I) catalysts were not seen. reaction does proceed initial 1,3-transposition their corresponding conjugated 1,3-diynone isomers. If methylamine is added, N-methyl-4-pyridones are exclusively 69-79% yields an analogous hydroamination/Au-catalyzed 6-endo pathway.

Язык: Английский

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One-Pot Synthesis of Functionally Enriched Benzo[b]fluorenones: An Eco-Friendly Embedment of Diverse 1-Indanones into o-Bis-Ynones

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(2), С. 933 - 943

Опубликована: Янв. 5, 2023

An efficient, base-promoted, one-pot, metal-free, open-flask synthesis of diverse, functionally enriched benzo[b]fluoren-11-ones has been discovered, and wide applicability this exceptionally simple protocol with green flavors scoped. This proceeds via an unanticipated, tandem, double-aldol condensation between in situ-generated 1-indanone dianions o-bis-ynones to furnish harboring as many six variegated substituents on their tetracyclic framework. methodology also amplified access heterocyclic analogues 2- 4-azabenzo[b]fluorenones extended mixed linear-angular annulated pentacyclic dibenzo[a,h]fluoren-13-one.

Язык: Английский

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Comprehensive Overview of Homogeneous Gold-Catalyzed Transformations of π-Systems for Application Scientists

Catalysts, Год журнала: 2023, Номер 13(6), С. 921 - 921

Опубликована: Май 23, 2023

We present an overview of fundamental catalytic reactions nucleophiles with π-systems in relation to gold chemistry. examples gold-activated π-systems, alkynyl or allenyl moieties, and the regulation their reactivity due presence electron-donating -withdrawing group. The describe furnished hard-to-reach heterocyclic building blocks for medicinal chemistry purposes. Important gold(I) gold(III) complexes that are used as catalysts presented. examine activation such using corresponding divergent transformations. provide catalysis catalyst other metal (Pt, Ag, Pd, Rh, Sc, Cu) by changing ligands complexes. also discuss role solvent, counterions additives gold(I)-catalyzed reactions. mention, a few cases, characteristic experimental computational studies these gold-catalyzed π-systems.

Язык: Английский

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Oxidative Ring-Opening Transformation of 5-Acyl-4-pyrones as an Approach for the Tunable Synthesis of Hydroxylated Pyrones and Furans

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(16), С. 11590 - 11602

Опубликована: Июль 28, 2023

A selective and tunable approach for oxidation of 4-pyrones has been developed via ring-opening transformations leading to various hydroxylated oxaheterocycles. The first step the strategy includes base-catalyzed epoxidation 5-acyl-4-pyrones in presence hydrogen peroxide effective synthesis pyrone epoxides high yields. bearing CO2Et group are reactive molecules that can undergo both oxirane deformylation produce 2-pyrones or 4-pyrones. acid-promoted transformation led 3-hydroxy-4-pyrones (24-76% yields), whereas K2CO3-catalyzed process 2-carbethoxy-4-pyrone proceeded as an attack alcohol at C-3 position give functionalized 6-acyl-5-hydroxy-2-pyrones (27-87% yields). reaction 2-aryl-4-pyrone was followed by ring contraction dearoylation 3-hydroxyfuran-2-carbaldehydes 42-80% 3-aroylchromone flavonols 3-hydroxybenzofuran-2-carbaldehyde acidic basic conditions, respectively. prepared heterocycles demonstrated reactivity further low cytotoxicity promising fluorophores UV filters.

Язык: Английский

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Tandem Michael–anti-Michael Addition-Mediated Orthogonal Strapping of Diynones: Regioselective Spirocyclopentannulation of Oxindoles and Pyrazolones and DFT Validation

The Journal of Organic Chemistry, Год журнала: 2021, Номер 87(1), С. 884 - 891

Опубликована: Дек. 23, 2021

An efficient protocol involving the transformation of sequentially generated recursive anions from heterocyclic precursors to orthogonally strap diynones through one pot transition-metal-free spirocyclopentannulation has been devised, employing oxindoles and pyrazolones as prototypical platforms. Insights into these regioselective tandem Michael–anti-Michael processes have gleaned DFT calculations.

Язык: Английский

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