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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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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Contemporary Approaches for Amide Bond Formation

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(24), P. 4359 - 4391

Published: Nov. 7, 2023

Abstract Amide bond construction has garnered significant interest in recent decades due to amides being one of the most prevalent functional groups among bioactive molecules. Out thirty‐seven new drugs approved by FDA 2022, eleven are small molecules containing at least amide bond. Additionally, there nineteen large as drugs, some which have peptide structures, and therefore, also bear bonds. In years, multiple teams embraced challenge developing more efficient methods for formation. This dedication led numerous publications appearing monthly prestigious journals, showcasing advancements this field. The primary goal review is present viable strategies constructing It crucial differentiate between formation synthesis; hence, focus on describing specific forming C(O)−N particular, concentrates developed within last six years. There a particular emphasis approaches that consider thought process when selecting starting materials groups. approach ensures coverage all common chemical transformations yield

Language: Английский

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Amide C–N bonds activation by A new variant of bifunctional N-heterocyclic carbene

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Jan. 12, 2024

Abstract We report an organocatalyst that combines a triazolium N-heterocyclic carbene (NHC) with squaramide as hydrogen-bonding donor (HBD), which can effectively catalyze the atroposelective ring-opening of biaryl lactams via unique amide C–N bond cleavage mode. The free species attacks carbonyl, forming axially chiral acyl-azolium intermediate. Various amines be accessed by this methodology up to 99% ee and yield. By using mercaptan catalyst turnover agent, resulting thioester synthon transformed into several interesting atropisomers. Both control experiments theoretical calculations reveal crucial role hybrid NHC-HBD skeleton, activates H-bonding brings it spatially close centre. This discovery illustrates potential chimera demonstrates complementary strategy for activation manipulation.

Language: Английский

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Highly Chemoselective Transamidation of Unactivated Tertiary Amides by Electrophilic N−C(O) Activation by Amide‐to‐Acyl Iodide Re‐routing

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(24)

Published: March 31, 2022

The challenging transamidation of unactivated tertiary amides has been accomplished via cooperative acid/iodide catalysis. Most crucially, the method provides a novel manifold to re-route reactivity N,N-dialkyl through reactive acyl iodide intermediates, thus reverting classical order carboxylic acid derivatives. This direct route amide-to-amide bond interconversion with excellent chemoselectivity using equivalent amounts amines. combination and identified as essential factor activate amide C-N electrophilic catalytic activation, enabling production new desired transamidated products wide substrate scope both amines, including late-stage functionalization complex APIs (>80 examples). We anticipate that this powerful activation mode bonds will find broad-ranging applications in chemical synthesis.

Language: Английский

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Classes of Amides that Undergo Selective N–C Amide Bond Activation: The Emergence of Ground-State Destabilization

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 88(19), P. 13371 - 13391

Published: Sept. 2, 2022

Ground-state destabilization of the N–C(O) linkage represents a powerful tool to functionalize historically inert amide bond. This burgeoning reaction manifold relies on availability bond precursors that participate in weakening nN → π*C=O conjugation through N–C twisting, N pyramidalization, and electronic delocalization. Since 2015, acyl activation ground-state has been achieved by transition-metal-catalyzed oxidative addition bond, generation radicals, transition-metal-free addition. Perspective summarizes contributions our laboratory development new ground-state-destabilized enabled twist synthetic utility amides cross-coupling reactions reactions. The use as electrophiles enables plethora previously unknown transformations such coupling, decarbonylative radical coupling forge C–C, C–N, C–O, C–S, C–P, C–B bonds. Structural studies activated catalytic systems developed past decade enable view change from "traditionally inert" "readily modifiable" functional group with continuum reactivity dictated destabilization.

Language: Английский

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Ni‐Catalyzed Divergent Synthesis of 2‐Benzazepine Derivatives via Tunable Cyclization and 1,4‐Acyl Transfer Triggered by Amide N‐C Bond Cleavage

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(25)

Published: April 6, 2022

Abstract Ligand‐directed divergent synthesis can transform common starting materials into distinct molecular scaffolds by simple tuning different ligands. This strategy enables the rapid construction of structurally rich collection small molecules for biological evaluation and reveals novel modes catalytic transformation, representing one most sought‐after challenges in synthetic chemistry. We herein report a Ni‐catalyzed ligand‐controlled tunable cyclization/cross‐couplings pharmacologically important 2‐benzazepine frameworks. The bidentate ligand facilitates nucleophilic addition aryl halides to amide carbonyl, followed 1,4‐acyl transfer cross‐coupling obtain 2‐benzazepin‐5‐ones benzo[c]pyrano[2,3‐e]azepines. tridentate promotes selective 7‐ endo cyclization/cross‐coupling access 2‐benzazepin‐3‐ones. protocol operates under mild reaction conditions with cyclization patterns that be easily modulated through backbone.

Language: Английский

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Palladium-Catalyzed [3 + 2] Annulation of Aromatic Amides with Maleimides through Dual C–H Activation

Organic Letters, Journal Year: 2023, Volume and Issue: 25(13), P. 2190 - 2195

Published: March 26, 2023

A palladium-catalyzed [3 + 2] annulation of substituted aromatic amides with maleimides providing tricyclic heterocyclic molecules in good to moderate yields through weak carbonyl chelation is reported. The reaction proceeds via a dual C-H bond activation where the first takes place selectively at benzylic position followed by second meta afford five-membered cyclic ring. An external ligand Ac-Gly-OH has been used succeed this protocol. plausible mechanism proposed for reaction.

Language: Английский

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Dual Nickel/Photoredox‐Catalyzed Asymmetric Carbamoylation of Benzylic C(sp³)−H Bonds

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(12)

Published: Jan. 12, 2024

Abstract Radical‐mediated Hydrogen Atom Abstraction of Csp 3 −H bonds has become a powerful tool for the asymmetric functionalization organic feedstocks. Here, we present an synthesis α ‐aryl amides via carbamoylation alkylarenes with isocyanates as electrophiles. The synergistic combination photoredox and chiral nickel‐catalyst, enables use readily available neutral reagents under mild reaction conditions provides straightforward access to pharmacologically relevant motifs in enantiomerically pure form.

Language: Английский

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Chemodivergent transformations of amides using gem-diborylalkanes as pro-nucleophiles

Nature Communications, Journal Year: 2020, Volume and Issue: 11(1)

Published: June 19, 2020

Abstract Amides are versatile synthetic building blocks and their selective transformations into highly valuable functionalities much desirable in the chemical world. However, diverse structure generally high stability of amides make challenging. Here we disclose a chemodivergent transformation primary, secondary tertiary by using 1,1-diborylalkanes as pro-nucleophiles. In general, B-O elimination occurs for lactams to generate enamine intermediate, while undergo B-N enolate intermediate. Various situ electrophilic trapping those intermediates allows chemoselective synthesis α-functionalized ketones, β-aminoketones, enamides, β-ketoamides, γ-aminoketones, cyclic amines from secondary, lactams. The key these is enolization effect after addition α-boryl carbanion amides.

Language: Английский

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