Selective Decarbonylation via Transition-Metal-Catalyzed Carbon–Carbon Bond Cleavage

Chemical Reviews, Journal Year: 2020, Volume and Issue: 121(1), P. 365 - 411

Published: June 16, 2020

Transition-metal-catalyzed decarbonylation via carbon–carbon bond cleavage is an essential synthetic methodology. Given the ubiquity of carbonyl compounds, selective decarbonylative process offers a distinct strategy using groups as "traceless handles". This reaction has been significantly developed in recent years many respects, including catalytic system development, mechanistic understanding, substrate scope, and application synthesis complex functional molecules. Therefore, this review aims to summarize progress on transition-metal-catalyzed process, from discovery new transformations understanding mechanisms, reveal great achievements potentials field. The contents are categorized by type chemical process. main challenges opportunities also examined with goal expanding range reactions.

Language: Английский

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Mechanistic Aspects of the Palladium‐Catalyzed Suzuki‐Miyaura Cross‐Coupling Reaction

Chemistry - A European Journal, Journal Year: 2021, Volume and Issue: 27(54), P. 13481 - 13493

Published: July 16, 2021

The story of C-C bond formation includes several reactions, and surely Suzuki-Miyaura is among the most outstanding ones. Herein, a brief historical overview insights regarding reaction mechanism provided. In particular, catalytically active species probably main concern, thus preactivation in competition with, or even assumes role rate determining step (rds) overall reaction. Computational chemistry key identifying rds leading to milder conditions on an experimental level by means predictive catalysis.

Language: Английский

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Acyl Fluorides in Late‐Transition‐Metal Catalysis

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(2), P. 574 - 594

Published: April 10, 2019

Abstract In this Review, we summarize the current state of art in late‐transition‐metal‐catalyzed reactions acyl fluorides, covering both their synthesis and further transformations. organic reactions, relationship between stability reactivity starting substrates is usually characterized by a trade‐off. Yet, fluorides display very good balance these properties, which mostly due to moderate electrophilicity. Thus, (RCOF) can be used as versatile building blocks transition‐metal‐catalyzed for example, an “RCO” source coupling “R” decarbonylative “F” fluorination reactions. Starting from cleavage C−F bond various transformations are accessible, including C−C, C−H, C−B, bond‐forming that catalyzed transition‐metal catalysts contain Group 9–11 metals Co, Rh, Ir, Ni, Pd, or Cu.

Language: Английский

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Nickel and Palladium Catalysis: Stronger Demand than Ever

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(2), P. 1180 - 1200

Published: Jan. 5, 2022

Key similarities and differences of Pd Ni in catalytic systems are discussed. Overall, catalyze a vast number similar C–C C–heteroatom bond-forming reactions. However, the smaller atomic radius lower electronegativity Ni, as well more negative redox potentials low-valent species, often provide higher reactivity oxidative addition or insertion reactions persistence alkyl-Ni intermediates against β-hydrogen elimination, thus enabling activation reluctant electrophiles, including alkyl electrophiles. Another key point relates to stability open-shell electronic configurations Ni(I) Ni(III) compared with Pd(I) Pd(III). Nickel very involve interconvertible Ni(n+) active species variable oxidation states (Ni(0), Ni(I), Ni(II), Ni(III)). In contrast, involving Pd(III) still relatively less developed may require facilitation by special ligands merging photo- electrocatalysis. high Pd(n+) ensure their facile reduction Pd(0) under assistance numerous reagents solvents, providing concentrations molecular Pd1(0) complexes that can reversibly aggregate into Pdn clusters nanoparticles form cocktail Pdn(0) various nuclearities (i.e., values "n"). Ni(0) strong reductants; they sensitive deactivation air other oxidizers and, consequence, operate at catalyst loadings than palladium same The ease robustness versatility for catalysis, whereas variety enables diverse uncommon reactivity, albeit requiring efforts stabilization nickel systems. As discussion, we note easily "cocktail particles" different but (Pd1, Pdn, NPs), behave species" is stable nuclearities. Undoubtedly, there stronger demand ever not only develop improved efficient catalysts also understand mechanisms

Language: Английский

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Acyclic Twisted Amides

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(20), P. 12746 - 12783

Published: Aug. 18, 2021

In this contribution, we provide a comprehensive overview of acyclic twisted amides, covering the literature since 1993 (the year first recognized report on amides) through June 2020. The review focuses classes amides and their key structural properties, such as amide bond twist nitrogen pyramidalization, which are primarily responsible for disrupting

Language: Английский

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Carbene and photocatalyst-catalyzed decarboxylative radical coupling of carboxylic acids and acyl imidazoles to form ketones

Nature Communications, Journal Year: 2022, Volume and Issue: 13(1)

Published: May 23, 2022

The carbene and photocatalyst co-catalyzed radical coupling of acyl electrophile a precursor is emerging as attractive method for ketone synthesis. However, previous reports mainly limited to prefunctionalized precursors two-component coupling. Herein, an N-heterocyclic catalyzed decarboxylative carboxylic acids imidazoles disclosed, in which the are directly used precursors. could also be generated situ by reaction acid with CDI thus furnishing formally two acids. In addition, successfully extended three-component using alkene third partner via relay process. mild conditions, operational simplicity, use reacting partners make our powerful strategy construction complex ketones from readily available starting materials, late-stage modification natural products medicines.

Language: Английский

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[Pd(NHC)(acac)Cl]: Well-Defined, Air-Stable, and Readily Available Precatalysts for Suzuki and Buchwald–Hartwig Cross-coupling (Transamidation) of Amides and Esters by N–C/O–C Activation

Organic Letters, Journal Year: 2019, Volume and Issue: 21(9), P. 3304 - 3309

Published: April 16, 2019

A general class of well-defined, air-stable, and readily available Pd(II)-NHC precatalysts (NHC = N-heterocyclic carbene) for Suzuki Buchwald–Hartwig cross-coupling amides (transamidation) esters by selective N–C/O–C cleavage is reported. Since these are highly active the easiest to synthesize, study clearly suggests that [Pd(NHC)(acac)Cl] should be routinely included during development new methods. An assay in situ screening NHC salts this manifold presented.

Language: Английский

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Synergistic Activation of Amides and Hydrocarbons for Direct C(sp³)–H Acylation Enabled by Metallaphotoredox Catalysis

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 59(39), P. 16933 - 16942

Published: June 17, 2020

Abstract The utilizations of omnipresent, thermodynamically stable amides and aliphatic C(sp 3 )−H bonds for various functionalizations are ongoing challenges in catalysis. In particular, the direct coupling between two functional groups has not been realized. Here, we report synergistic activation challenging bonds, amide C−N unactivated )−H, via metallaphotoredox catalysis to directly acylate C−H utilizing as readily accessible acyl surrogates. N‐acylsuccinimides served efficient reagents streamlined synthesis synthetically useful ketones from simple substrates. Detailed mechanistic investigations using both computational experimental studies were performed construct a detailed complete catalytic cycle. origin superior reactivity over other more reactive sources such chlorides was found be an uncommon reaction pathway which commences with prior oxidative addition substrate.

Language: Английский

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Light‐Driven Carbene Catalysis for the Synthesis of Aliphatic and α‐Amino Ketones

Angewandte Chemie International Edition, Journal Year: 2021, Volume and Issue: 60(33), P. 17925 - 17931

Published: June 7, 2021

Single-electron N-heterocyclic carbene (NHC) catalysis has gained attention recently for the synthesis of C-C bonds. Guided by density functional theory and mechanistic analyses, we report light-driven aliphatic α-amino ketones using single-electron NHC operators. Computational experimental results reveal that reactivity key radical intermediate is substrate-dependent can be modulated through steric electronic parameters NHC. Catalyst potential harnessed in visible-light driven generation an acyl azolium species undergoes selective coupling with various partners to afford diverse ketone products. This methodology showcased direct late-stage functionalization amino acids pharmaceutical compounds, highlighting utility

Language: Английский

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Recent Methodologies That Exploit Oxidative Addition of C–N Bonds to Transition Metals

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(21), P. 12738 - 12759

Published: Oct. 19, 2020

The activation of σ-bonds by transition metals underpins a wide range methods for the synthesis complex molecules. Within this context, C–N bond has emerged recently as powerful strategy preparation or utilization nitrogen-containing compounds, due to prevalence bonds in organic compounds. A key challenge area is that most are relatively inert, and makes their difficult task. Since turn millennium number published articles regarding grown exponentially, providing important improvements methodologies such transformations. Indeed, several distinct strategies have been developed achieve activation. common exploited either strain release quaternization nitrogen center, while other state-of-the-art strategies, oxidative addition neutral use directing groups, also appeared. Despite considerable progress, deeper insight into mechanisms atom economy still required field advance. In Perspective we give an overview advances catalytic where achieved metals.

Language: Английский

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