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

ChemCatChem, Год журнала: 2024, Номер 16(4)

Опубликована: Янв. 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.

Язык: Английский

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Catalyst-free electro-photochemical insertion reactions of carbene anion radicals by convergent paired electrolysis

Cell Reports Physical Science, Год журнала: 2024, Номер 5(5), С. 101944 - 101944

Опубликована: Май 1, 2024

Paired electrolysis is an energy-efficient electrochemical reaction where both anodic and cathodic electron flow directly induces product formation with maximum faradaic efficiency. Herein we report a metal-free convergent pair electro-photochemical strategy to generate radical cation anion that resulted in the N-alkylation of various N-heterocycles, amines, sulfonamides. The also facilitated site-selective CH-alkylation benzo fused morpholine, indolines, OH- SH- alkylation phenols thiophenols aryl diazo esters. Mild condition such as 5 mA constant current W blue LED were sufficient complete within 2 h. Late-stage APIs sulfadiazines privileged scaffolds like sulfonamides diazepanes have been achieved successfully. This paired photo-electrolysis establishes new way achieve important reactions better productivity shorter time over existing strategies.

Язык: Английский

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I₂‐Promoted Oxidative Annulation of Deoxybenzoin‐Chalcone Adduct: Temperature‐Controlled Access to Tetrasubstituted 2,3‐trans‐Dihydrofurans and Furans

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(12), С. 2691 - 2695

Опубликована: Апрель 23, 2024

Abstract Tetrasubstituted 2,3‐ trans ‐dihydrofuran and furan are important heterocyclic scaffolds in natural product, bioorganic medicinal chemistry as well material science. The synthesis of both these heterocycles starting from common readily available materials challenging. We found that situ generated deoxybenzoin‐chalcone Michael adducts underwent oxidative annulation upon heating with molecular iodine DMSO to provide selectively ‐dihydrofurans at 80 °C furans 120 °C.

Язык: Английский

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Asymmetric Synthesis of Tetrahydrofurans with Vicinal Stereocenters by Rh^II/Ru^II Relay Catalysis

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Апрель 25, 2025

CpRu-catalyzed asymmetric allylic alkylation serves as a versatile synthetic tool but remains underexplored. Herein, we report relay system combining achiral Rh2(OAc)4 and chiral pyridine-oxazoline-ligated Cp*Ru catalyst for coupling of cinnamyl chlorides with diazo esters, generating silyl enol ethers in situ key nucleophilic intermediates. This strategy affords tetrahydrofuran derivatives two vicinal stereocenters. Catalyst compatibility, excellent regioselectivity, good enantioselectivity highlight its potential. Computational studies reveal the crucial role Ru-centered chirality reaction control.

Язык: Английский

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Palladium-Catalyzed Carbene Migratory Insertion/Carbonylation Cascade Reaction: Synthesis of 2-Indolones with a C3 All-Carbon Quaternary Center

Organic Letters, Год журнала: 2022, Номер 24(5), С. 1237 - 1242

Опубликована: Янв. 31, 2022

An attractive palladium-catalyzed three-component reaction of ortho-amino aryl diazo esters, allyl carboxylates, and carbon monoxide (CO) has been developed. This catalytic system rendered domino carbene migratory insertion carbonylation. Remarkably, 2-indolones 3 with a C3 all-carbon quaternary center can be selectively obtained in good to excellent yields via one-pot synthesis, which two different C-C bonds one C-N bond were formed straightforward manner.

Язык: Английский

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Cooperative Rh(II)/Pd(0) Dual‐Catalyzed gem‐Difunctionalization of α‐Diazo Carbonyl Compounds: Construction of Quaternary Carbon Centers

European Journal of Organic Chemistry, Год журнала: 2022, Номер 2022(26)

Опубликована: Май 24, 2022

Abstract The efficient construction of quaternary carbon centers is a challenging task due to their enhanced structural complexity. Although the catalytic gem‐ difunctionalization α ‐diazo carbonyl compounds via metal‐carbenoids well‐documented, developing new methods access which are difficult or unattainable in monocatalysis highly desirable. Dual catalysis where two different catalysts work concurrently has emerged as powerful strategy achieve reactivity and selectivity. In this review, we highlight recent advances cooperative Rh(II)/Pd(0) dual for centers, focusing on synthetic utility stable ‐diazo‐ β ‐keto‐esters allylic carboxylates. Additionally, several asymmetric dual‐catalyzed transformations generating chiral also discussed.

Язык: Английский

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Dual Rh(II)/Pd(0) Relay Catalysis Involving Sigmatropic Rearrangement Using N-Sulfonyl Triazoles and 2-Hydroxymethylallyl Carbonates

Organic Letters, Год журнала: 2022, Номер 24(38), С. 6951 - 6956

Опубликована: Сен. 19, 2022

Dual Rh(II)/Pd(0) relay catalysis of N-sulfonyl triazoles and 2-hydroxymethylallyl carbonates has been developed, which affords pyrrolidines in moderate to good yields with high diastereoselectivities. The reaction proceeds via a mechanism involving O-H insertion onto the α-imino Rh(II)-carbene, [3,3]-sigmatropic rearrangement, dipole formation through Pd(0)-catalyzed decarboxylation, intramolecular N-allylation, leading multiple bonds one-pot operation.

Язык: Английский

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Rh(II)/Pd(0) Dual Catalysis: Interception of Ammonium Ylide with Allyl Palladium to Construct 2,2-Disubstituted Tetrahydroquinoline Derivatives

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(13), С. 9496 - 9504

Опубликована: Июнь 10, 2023

New synthetic methods to construct 2,2-disubstituted tetrahydroquinoline derivatives are of significant value in pharmaceutical chemistry. Herein, a Rh(II)/Pd(0) dual-catalyzed diazo α-aminoallylation reaction has been developed between allylpalladium(II) and ammonium ylides derived from the Rh2(OAc)4-mediated intramolecular N-H bond insertion compounds, affording various good yields up 93% with high chemoselectivities under mild conditions. A substrate scope investigation reveals broad ester substituent tolerance, control experiments provide basis for proposed mechanism.

Язык: Английский

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Dual Catalysis in Rhodium(II) Carbenoid Chemistry

European Journal of Organic Chemistry, Год журнала: 2022, Номер 2022(27)

Опубликована: Янв. 21, 2022

Abstract Dual catalysis represents an alternative archetype in carbene chemistry that surpasses traditional single catalyst systems. By employing dual systems, one can improve the efficiency of existing reactions and enable new chemical transformations. Reactions involving synergistic are increasingly valuable as they offer convenient strategies for synthesizing challenging quaternary carbon centers bioactive core structures. This review article focuses on trapping diazo‐derived, rhodium (II) zwitterionic intermediates with varying electrophiles such Michael acceptors, alkynes, π‐allyl Pd(II) complexes, Nicholas intermediate.

Язык: Английский

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Carboxylic Acid O–H Insertion Reaction of β-Ester Diazos Enabling Synthesis of β-Acyloxy Esters

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(22), С. 15483 - 15491

Опубликована: Ноя. 10, 2022

Generation of non-stabilized β-ester diazos and their applications in carboxylic acid O–H insertion reactions have been reported, which afford β-acyloxy esters excellent yield. Varieties aryl- alkyl-substituted are well tolerated this reaction under mild convenient conditions. Moreover, structural modification the natural product molecular drug can also be achieved reaction. This protocol not only realizes involving unstable but provides an efficient strategy for synthesis esters.

Язык: Английский

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