Multiligand Enabled, Copper-Catalyzed Hiyama Coupling of Arylsilanes with Unactivated Secondary Alkyl Halides: Reaction Development and Mechanistic Insights

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

A multiligand-involved Cu catalysis offers an efficient Hiyama coupling of arylsilanes with unactivated alkyl halides, where copper NHC and phenanthroline ligands were account for C(sp 2 )–Si activation )–C(sp 3 ) formation, respectively.

Language: Английский

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Dirhodium–Palladium Dual-Catalyzed [1 + 1 + 3] Annulation to Heterocycles Using Primary Amines or H₂O as the Heteroatom Sources

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

The ever-increasing demand in chemical biology and medicinal research requires the development of new synthetic methods for rapid construction libraries heterocycles from simple raw materials. In this context, utilization primary amines or H2O as N- O-sources assembly a heterocyclic ring skeleton is highly desirable viewpoint atom- step-economy. Herein, we describe efficient three-component reaction diazo, allylic diacetates, commercially available anilines (or H2O) to access structurally diverse pyrrolidine tetrahydrofuran derivatives. This formal [1 + 1 3] annulation features high efficiency, good yields, broad functional group compatibility, making it versatile robust platform (formal) synthesis several important bioactive molecules. Mechanistic studies suggested that dirhodium–palladium bimetallic relay catalysis should play key role successive steps current reaction, including sequential carbene insertion into X–H bond double substitutions, thus allowing building up molecular complexity these

Language: Английский

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Overview of Transition Metal Catalyzed Multicomponent Reactions Based on Trapping of Allylic Electrophiles

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(4)

Published: Jan. 11, 2024

Abstract Multicomponent reactions provide an excellent approach toward quaternary carbon centres utilizing convergent chemical in a highly selective manner under one‐pot conditions. The reactivity of substrates and metal catalysts is carefully controlled, precluding the formation side‐products. In this context, transition catalyzed onium ylides generated via diazo precursors nucleophiles with third component (an electrophile) have garnered significant attention. Using allylic precursor as electrophilic partner provides opportunities to construct all‐carbon centres. Furthermore, presence allyl fragment multicomponent product serves pivotal handle for carrying out subsequent modifications. Several recent studies employed Rh, Pd, dual Rh/Pd catalytic systems involving alkylation that proceed synergistic or relay pathway. Although not significantly successful, few cases, asymmetric induction achieved through chiral phosphoric acids phosphine ligands. Limited substrate catalyst scope underlying mechanistic complexities posed formidable challenges, slowing advancement reactions. This review details using readily available like compounds, carbonates, (R‐OH, R‐NH 2 , etc .) forming complex organic compounds. Our primary objective discuss issues may facilitate progress field.

Language: Английский

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Ligand Relay for Nickel‐Catalyzed Decarbonylative Alkylation of Aroyl Chlorides

Advanced Science, Journal Year: 2023, Volume and Issue: 11(9)

Published: Dec. 13, 2023

Abstract Transition metal‐catalyzed direct decarboxylative transformations of aromatic carboxylic acids usually require high temperatures, which limit the substrate's scope, especially for late‐stage applications. The development selective decarbonylative acid derivatives, most fundamental aroyl chlorides, with stable and cheap electrophiles under mild conditions is highly desirable meaningful, but remains challenging. Herein, a strategy nickel‐catalyzed alkylation chlorides via phosphine/nitrogen ligand relay reported. simple phosphine found essential decarbonylation step, while nitrogen promotes cross‐electrophile coupling. Such system can effectively orderly carry out catalytic process at room temperature, utilizing easily available as an aryl electrophile reductive alkylation. This discovery provides new coupling, features operationally simple, conditions, excellent functional group tolerance. approach applied to methylation various pharmaceuticals. Extensive experiments are carried provide insights into reaction pathway support process.

Language: Английский

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Stereoselective gem-Difunctionalization of Diazo Compounds with Vinyl Sulfoxonium Ylides and Thiols via Metalloradical Catalysis

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2805 - 2815

Published: Feb. 8, 2024

Multicomponent reactions that involve carbenes with nucleophiles and electrophiles have demonstrated broad applications in synthetic chemistry. However, because of the high reactivity transient carbenes, involving two carbene precursors nucleophile presence a metal catalyst remain unexplored. Herein, three-component stereoselective gem-difunctionalization diazo compounds thiols vinyl sulfoxonium ylide is disclosed via Co(II)-based metalloradical catalysis. The key aspect present strategy to exploit intrinsic difference ylides thiol catalysts. Doyle–Kirmse rearrangement sulfonium involves convergent assembly situ-generated intermediates, such as allyl sulfide α- metalloalkyl radical complex, provide expeditious access tertiary scaffolds. Combined experimental quantum chemical calculations unveil intricate mechanism this reaction. Furthermore, theoretical studies on noncovalent interactions selectivity-determining transition states explain origin experimentally obtained diastereoselectivity.

Language: Английский

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Electron Deficient Ir–O Bonds Promote Heterogeneous Ir-Catalyzed Anti-Markovnikov Hydroboration of Alkenes under Mild Neat Conditions

Nano Letters, Journal Year: 2024, Volume and Issue: 24(17), P. 5165 - 5173

Published: April 17, 2024

Tuning electronic characteristics of metal–ligand bonds based on reaction pathways to achieve efficient catalytic processes has been widely studied and proven be feasible in homogeneous catalysis, but it is scarcely investigated heterogeneous catalysis. Herein, we demonstrate the regulation configuration Ir–O an Ir single-atom catalyst according borane activation mechanism. Ir1/Ni(OH)x are found more electron-poor than those Ir1/NiOx. Despite mild solvent-free conditions ambient temperature, exhibits outstanding performance for hydroboration alkenes, furnishing desired alkylboronic esters with a turnover frequency value ≤3060 h–1 99% anti-Markovnikov selectivity, which significantly better that Ir1/NiOx (42 h–1). It further as active centers oxidative so benefit H–B bond reductive pinacolborane.

Language: Английский

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Rh(II)/Pd(0) Dual-Catalyzed Regio-Divergent Three-Component Propargylic Substitution

JACS Au, Journal Year: 2023, Volume and Issue: 3(10), P. 2862 - 2872

Published: Sept. 25, 2023

Regio-divergent propargylic substitution to generate functionally diverse products from identical starting materials remains a formidable challenge, probably due the unpredictable regiochemical complexity. In practically, synthesis of α-quaternary propargylic-substituted is still much less developed, and preprepared nucleophiles are generally applied in this type reaction with substrates, which limits efficiency diversity obtained products. Herein, we disclose unprecedented three-component α-diazo esters amines carbonates under dirhodium/palladium dual catalysis. The key success multicomponent avoid two-component side reactions through tandem process dirhodium(II)-catalyzed carbene insertion palladium-catalyzed regiodivergent substitution. judicious selection diphosphine (dppf) or monophosphine (tBuBrettphos) as ligand crucial for different switchable way, 1,3-dienyl propargylated products, high regio- chemoselectivities.

Language: Английский

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Cobalt-Catalyzed Diester Formation with CO at Atmospheric Pressure via Three-Component Reactions

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 28, 2025

We propose a cobalt-catalyzed three-component reaction conducted under mild conditions. Following the carbonyl insertion at atmospheric pressure, proceeds via nucleophilic attack by alcohols to form diesters. Notably, scope of reagents can be extended include range anilines. Furthermore, products this transformation serve as crucial synthetic building blocks for diverse organic synthesis processes, with subsequent derivatizations yielding promising results.

Language: Английский

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Visible‐Light‐Driven Multicomponent Reactions of Diazosulfonium Triflates with Amines and CS₂ or CO₂: Direct Synthesis of Bis‐Dithiocarbamates/Carbamates

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: May 19, 2025

Comprehensive Summary Visible light‐induced transformation of CO 2 and CS into value‐added products has attracted worldwide attention because it mimics nature. In this context, although visible‐light‐induced direct synthesis dithiocarbamates carbamates employing SO as a C1 source been reported, all these reactions are limited to the preparation S ‐alkyl mono‐dithiocarbamates O mono‐carbamates. Herein, we report visible‐light photoredox‐catalyzed multicomponent reaction diazosulfonium triflates with amines or . Mechanistic studies indicate that diazomethyl radicals might be generated key intermediates, thus providing direction for application other radical acceptors.

Language: Английский

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Cobalt‐Catalyzed Difunctionalization of Styrenes via Ligand Relay Catalysis^†

Chinese Journal of Chemistry, Journal Year: 2023, Volume and Issue: 41(24), P. 3633 - 3638

Published: Aug. 29, 2023

Comprehensive Summary Here, we report a cobalt‐catalyzed sequential dehydrogenative Heck silylation/hydroamination of styrenes with hydrosilane and diazo compound to access 1‐amino‐2‐silyl compounds excellent regioselectivity. This difunctionalization reaction could undergo smoothly using 1 mol% catalyst loading good functional group tolerance. Not only di‐ tri‐substituted hydrosilanes, but also alkoxysilane is suitable, which does explore the scope family compounds. The ligand relay phenomenon between neutral tridentate NNN anionic observed for first time via absorption spectral analysis in this one‐pot, two‐step transformations. primary mechanism has been proposed based on control experiments.

Language: Английский

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