Unified approaches in transition metal catalyzed C(sp³)–H functionalization: recent advances and mechanistic aspects

Chemical Society Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Direct alteration of unactivated C–H bonds organic building blocks.

Language: Английский

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Cooperative Fe/Co-Catalyzed Remote Desaturation for the Synthesis of Unsaturated Amide Derivatives

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(7), P. 4985 - 4992

Published: Feb. 6, 2024

Unsaturated amides represent common functional groups found in natural products and bioactive molecules serve as versatile synthetic building blocks. Here, we report an iron(II)/cobalt(II) dual catalytic system for the syntheses of distally unsaturated amide derivatives. The transformation proceeds through iron nitrenoid-mediated 1,5-hydrogen atom transfer (1,5-HAT) mechanism. Subsequently, radical intermediate undergoes hydrogen abstraction from vicinal methylene by a cobaloxime catalyst, efficiently yielding β,γ- or γ,δ-unsaturated derivatives under mild conditions. efficiency Co-mediated HAT can be tuned varying different auxiliaries, highlighting generality this protocol. Remarkably, desaturation protocol is also amenable to practical scalability, enabling synthesis carbamates ureas, which readily converted into various valuable molecules.

Language: Английский

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Hydrogen Atom Transfer (HAT)-Mediated Remote Desaturation Enabled by Fe/Cr–H Cooperative Catalysis

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(7), P. 4795 - 4802

Published: Feb. 8, 2024

An iron/chromium system (Fe(OAc)2, CpCr(CO)3H) catalyzes the preparation of β,γ- or γ,δ-unsaturated amides from 1,4,2-dioxazol-5-ones. acyl nitrenoid iron complex seems likely to be responsible for C–H activation. A cascade three H• transfer steps appears involved: (i) abstraction a remote bond by N, (ii) Cr and (iii) radical substituent Cr•. The observed kinetic isotope effects are consistent with proposed mechanism if formation is rate-determining step. Fe/Cr catalysts can also desaturate substituted 1,4,2-dioxazol-5-ones 3,5-dienamides.

Language: Английский

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Chiral Osmium(II)/Salox Species Enabled Enantioselective γ‐C(sp³)−H Amidation: Integrated Experimental and Computational Validation For the Ligand Design and Reaction Development

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(20)

Published: March 19, 2024

Abstract Herein, multiple types of chiral Os(II) complexes have been designed to address the appealing yet challenging asymmetric C(sp 3 )−H functionalization, among which Os(II)/Salox species is found be most efficient for precise stereocontrol in realizing amidation. As exemplified by enantioenriched pyrrolidinone synthesis, such tailored catalyst efficiently enables an intramolecular site‐/enantioselective amidation γ‐position dioxazolone substrates, benzyl, propargyl and allyl groups bearing various substituted forms are well compatible, affording corresponding γ‐lactam products with good er values (up 99 : 1) diverse functionality (>35 examples). The unique performance advantage developed system terms catalytic energy profile induction has further clarified integrated experimental computational studies.

Language: Английский

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Copper-catalyzed C–N cross-coupling for construction of alkylated N-cyanamide derivatives via nitrogen umpolung

Chem, Journal Year: 2024, Volume and Issue: 10(8), P. 2538 - 2549

Published: May 21, 2024

Language: Английский

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A Formal γ-C–H Functionalization of Carboxylic Acids Guided by Metal-Nitrenoids as an Unprecedented Mechanistic Motif

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(51), P. 28251 - 28263

Published: Dec. 15, 2023

Harnessing the key intermediates in metal-catalyzed reactions is one of most essential strategies development selective organic transformations. The nitrogen group transfer reactivity metal-nitrenoids to ubiquitous C–H bonds allows for diverse C–N bond formation furnish synthetically valuable aminated products. In this study, we present an unprecedented iridium and ruthenium nitrenoids generate remote carbocation intermediates, which subsequently undergo nucleophile incorporation, thus developing a formal γ-C–H functionalization carboxylic acids. Mechanistic investigations elucidated unique singlet metal-nitrenoid initiate abstraction γ-hydride form intermediate that eventually reacts with broad range carbon, nitrogen, oxygen nucleophiles, as well biorelevant molecules. Alternatively, same can lead deprotonation afford β,γ-unsaturated amides less nucleophilic solvent.

Language: Английский

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Visible-light-induced Fe(iii)-promoted reduction amidation of 1,4,2-dioxazol-5-one

New Journal of Chemistry, Journal Year: 2024, Volume and Issue: 48(30), P. 13654 - 13658

Published: Jan. 1, 2024

This method describes the iron-promoted amidation of dioxazolone under visible light to obtain aromatic/alkyl substituted amides.

Language: Английский

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Recent Advances in Nonprecious Metal Catalysis

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(9), P. 3524 - 3544

Published: Aug. 9, 2024

Developing catalytic reactions using nonprecious-metal to achieve various synthetic transformations remains a valuable pursuit the scientific community. As part of continuing review series that is published within precompetitive chemistry alliance between AbbVie, Boehringer Ingelheim and Pfizer, this article underscores wide-ranging uses Cu-, Co-, Fe-, Ni-catalysis. The significant uptick in NPMC-related publications signifies escalating curiosity among researchers investigate advance capabilities these metals.

Language: Английский

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Cooperative Fe/Co Catalyzed Remote Desaturation for the Synthesis of Unsaturated Amide Derivatives

Published: Dec. 20, 2023

Unsaturated amides represent common functional groups found in natural products and bioactive molecules, serving as versatile synthetic building blocks. Here, we report an iron(II)/cobalt(II) dual catalytic system for the syntheses of distally unsaturated amide derivatives. The transformation proceeds through iron nitrenoid-mediated 1,5-hydrogen atom transfer (1,5-HAT) mechanism. Subsequently, radical intermediate undergoes hydrogen abstraction from vicinal methylene by a cobaloxime catalyst, efficiently yielding β,γ- or γ,δ-unsaturated derivatives under mild conditions. efficiency Co-mediated HAT is tunable varying different auxiliaries, highlighting generality this protocol. Remarkably, desaturation protocol also amenable to practical scalability, enabling synthesis carbamates ureas which can be readily converted into various valuable molecules.

Language: Английский

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Chiral Osmium(II)/Salox Species Enabled Enantioselective γ‐C(sp³)−H Amidation: Integrated Experimental and Computational Validation For the Ligand Design and Reaction Development

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(20)

Published: March 19, 2024

Abstract Herein, multiple types of chiral Os(II) complexes have been designed to address the appealing yet challenging asymmetric C(sp 3 )−H functionalization, among which Os(II)/Salox species is found be most efficient for precise stereocontrol in realizing amidation. As exemplified by enantioenriched pyrrolidinone synthesis, such tailored catalyst efficiently enables an intramolecular site‐/enantioselective amidation γ‐position dioxazolone substrates, benzyl, propargyl and allyl groups bearing various substituted forms are well compatible, affording corresponding γ‐lactam products with good er values (up 99 : 1) diverse functionality (>35 examples). The unique performance advantage developed system terms catalytic energy profile induction has further clarified integrated experimental computational studies.

Language: Английский

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