Cobalt‐Catalyzed Enantioselective C−H Carbonylation towards Chiral Isoindolinones

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(10)

Опубликована: Янв. 11, 2024

Transition metal-catalyzed enantioselective C-H carbonylation with carbon monoxide, an essential and easily available C1 feedstock, remains challenging. Here, we disclosed unprecedented catalyzed by inexpensive readily cobalt(II) salt. The reactions proceed efficiently through desymmetrization, kinetic resolution, parallel affording a broad range of chiral isoindolinones in good yields excellent enantioselectivities (up to 92 % yield 99 ee). synthetic potential this method was demonstrated asymmetric synthesis biological active compounds, such as (S)-PD172938 (S)-Pazinaclone. resulting also serve ligands cobalt-catalyzed annulation alkynes construct phosphorus stereocenter.

Язык: Английский

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C–H bond functionalization by high-valent cobalt catalysis: current progress, challenges and future perspectives

Chemical Communications, Год журнала: 2021, Номер 57(83), С. 10827 - 10841

Опубликована: Янв. 1, 2021

Over the last decade, high-valent cobalt catalysis has earned a place in spotlight as valuable tool for C-H activation and functionalization. Since discovery of its unique reactivity, more attention been directed towards utilization an alternative to noble metal catalysts. In particular, Cp*Co(III) complexes, well simple Co(II) Co(III) salts combination with bidentate chelation assistance, have extensively used development novel transformations. this review, we demonstrated existing trends functionalization methodology using highlighted main challenges overcome, perspective directions, which need be further developed future.

Язык: Английский

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Indole Synthesis by Cobalt-Catalyzed Intramolecular Amidation via the Oxidatively Induced Reductive Elimination Pathway

ACS Catalysis, Год журнала: 2024, Номер 14(3), С. 1690 - 1698

Опубликована: Янв. 17, 2024

C–H bond activation and functionalization using high-valent cobalt catalysis typically involves a Co(III)/Co(I) catalytic cycle. Because of the lack evidence challenges associated with high reactivity instability Co(IV) intermediates, reports on mechanism investigation involving intermediacy are still underexplored. Herein, we report an efficient synthesis indole-2-carboxylic esters via intramolecular amidation α-amidoacrylates experimental computational studies reaction mechanism, which oxidatively induced reductive elimination from species.

Язык: Английский

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Metal‐Catalyzed C(sp²)−H Functionalization Processes of Phenylalanine‐ and Tyrosine‐Containing Peptides

European Journal of Inorganic Chemistry, Год журнала: 2021, Номер 2021(29), С. 2928 - 2941

Опубликована: Июнь 14, 2021

Abstract The site‐selective chemical diversification of biomolecules constitutes an unmet challenge capital importance within medicinal chemistry and biology. functionalization otherwise unreactive C−H bonds holds great promise for reducing the reliance on existing functional groups, thereby streamlining syntheses. Over last years, a myriad peptide labelling techniques featuring metal‐catalyzed reactions have been developed. Despite wealth reports in field, modification both phenylalanine (Phe) tyrosine (Tyr) compounds upon metal catalysis remain comparatively overlooked. This review highlights these promising tagging strategies, which generally occur through formation challenging 6‐membered metallacycles enable late‐stage peptides tailored fashion.

Язык: Английский

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Cobalt(II)-Catalyzed Activation of C(sp³)–H Bonds: Organic Oxidant Enabled Selective Functionalization

ACS Catalysis, Год журнала: 2022, Номер 12(3), С. 1650 - 1656

Опубликована: Янв. 13, 2022

Herein we develop a new "cobalt(II)/organic oxidant" catalytic system for the selective activation of 1°, 2°, and 3° C(sp3)–H bonds to construct C–N C–O bonds, respectively. The method highlights use an organic compound (TsNHOPiv or its analogues) as emerging oxidant thus provides flexible strategy preparation indoline benzoxazine derivatives. Attractive advantages this cobalt catalysis include simple operation, low cost, mild conditions, broad substrate scope. Furthermore, catalytically competent hydroxylamine-chelated organometallic Co(III)species was synthesized, providing deep insights into mechanism.

Язык: Английский

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Pd-catalyzed site-selective C(sp²)–H chalcogenation of amino acids and peptides using a picolinamide auxiliary

Organic Chemistry Frontiers, Год журнала: 2023, Номер 10(5), С. 1252 - 1262

Опубликована: Янв. 1, 2023

An efficient method for Pd-catalyzed site-selective C(sp 2 )–H chalcogenation of α-amino acids/peptides with disulfides and diselenides in moderate to good yields is presented.

Язык: Английский

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Co(III) Intermediates in Cobalt-Catalyzed, Bidentate Chelation Assisted C(sp2)-H Functionalizations

Inorganics, Год журнала: 2023, Номер 11(5), С. 194 - 194

Опубликована: Апрель 29, 2023

The C-H bond activation and functionalization is a powerful tool that provides efficient access to various organic molecules. cobalt-catalyzed oxidative has earned enormous interest over the past two decades. Since then, wide diversity of synthetic protocols have been published for C-C, C-Het, C-Hal formation reactions. To gain some insights into reaction mechanism, authors performed series experiments collected evidence. Several groups successfully isolated reactive Co(III) intermediates elucidate mechanism. In this review, we will summarize information concerning synthesized in cobalt-catalyzed, bidentate chelation assisted their reactivity based on current knowledge about general

Язык: Английский

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Palladium-Catalyzed Aminocarbonylation of (Hetero)aryl Iodides with α-Amino Acid Esters as Nucleophiles

The Journal of Organic Chemistry, Год журнала: 2022, Номер 87(12), С. 8005 - 8016

Опубликована: Июнь 3, 2022

We report palladium-catalyzed aminocarbonylation of (hetero)aryl iodides with α-amino acid esters as nucleophiles. The synthesized N-capped acids are biologically important building blocks. mild conditions provide products high enantioselectivity at 80 °C in 35 min. reactions performed under air a sealed vessel using chloroform an situ CO source. For the first time, regioselective carbonylation histidine is also presented.

Язык: Английский

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Pd‐Catalyzed Arylation and Benzylation of Tyrosine at the δ−C(sp²)−H and C(2) Positions: Expanding the Library of Unnatural Tyrosines

European Journal of Organic Chemistry, Год журнала: 2023, Номер 26(31)

Опубликована: Июнь 20, 2023

Abstract This paper describes Pd(II)‐catalyzed picolinamide‐directed intermolecular arylation and benzylation of remote δ −C(sp 2 )−H bond (C(2) position) the aryl ring in tyrosine derivatives expansion library unnatural tyrosine. Various racemic enantiopure bis C(2) ( ortho C−H) arylated benzylated were assembled good yields. Removal picolinoyl moiety after C(2)−H assembling tyrosine‐based peptides using tyrosines shown. Tyrosine biaryl amino acids are vital scaffolds medicinal chemistry. Correspondingly, this work is a contribution towards with biaryl‐ or terphenyl diarylmethane‐based scaffolds.

Язык: Английский

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Cobalt-Catalyzed C–H Bond Functionalization: a Personal Account

Synlett, Год журнала: 2025, Номер unknown

Опубликована: Апрель 29, 2025

Abstract The development of green and sustainable synthetic methods is great interest worldwide. Today the direct activation functionalization relatively inert C–H bonds one top fields in organic chemistry, this strategy already represents a more environmentally friendly approach due to its atom step economy compared alternative C–C C–Het bond-forming processes. Much progress has been made developing bond using noble-metal catalysts. Cobalt recently emerged as an attractive because it less toxic, cheaper, abundant than noble metals. This Account summarizes cobalt-catalyzed bond-functionalization that have developed during corresponding author’s research career. 1 Introduction Background 2 Bond Functionalization 8-Aminoquinoline Benzamides 3 Mechanistic Investigations Cobalt-Catalyzed, Aminoquinoline-Directed 4 C(sp2)–H Phosphinamides 5 Carbonylation Sulfonamides 6 Benzoic Acids 7 Phenylglycine Derivatives 8 Phenylalanine 9 Conclusion

Язык: Английский

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