Enantioselective C(sp³)–H Amidation of Thioamides Catalyzed by a Cobalt^III/Chiral Carboxylic Acid Hybrid System

Angewandte Chemie International Edition, Год журнала: 2018, Номер 58(4), С. 1153 - 1157

Опубликована: Ноя. 27, 2018

Abstract Recent advances in Cp x M III catalysis (M=Co, Rh, Ir) have enabled a variety of enantioselective C(sp 2 )−H functionalization reactions, but 3 is still largely unexplored. We describe an asymmetric amidation thioamides using achiral Co /chiral carboxylic acid hybrid catalytic system, which provides easy and straightforward access to chiral β‐amino thiocarbonyl carbonyl building blocks with quaternary carbon stereocenter.

Язык: Английский

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Diverse Approaches for Enantioselective C−H Functionalization Reactions Using Group 9 Cp^xM^III Catalysts

Chemistry - A European Journal, Год журнала: 2020, Номер 26(33), С. 7346 - 7357

Опубликована: Янв. 29, 2020

Transition-metal-catalyzed C-H functionalization reactions with Cp*MIII catalysts (M=Co, Rh, Ir) have found a wide variety of applications in organic synthesis. Albeit the intrinsic difficulties achieving catalytic stereocontrol using these due to their lack additional coordination sites for external chiral ligands and conformational flexibility Cp ligand, enantioselective Group 9 metal triad Cp-type been intensively studied since 2012. In this minireview, progress according type catalyst used are summarized discussed. The development Cpx complexes thereof, artificial metalloenzymes, carboxylate-assisted activations, alkylations assisted by carboxylic acids or sulfonates, transient directing groups

Язык: Английский

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Chiral Cyclopentadienyl Cobalt(III) Complexes Enable Highly Enantioselective 3d-Metal-Catalyzed C–H Functionalizations

Journal of the American Chemical Society, Год журнала: 2019, Номер 141(14), С. 5675 - 5680

Опубликована: Март 22, 2019

The synthesis of a set cobalt(III)-complexes equipped with trisubstituted chiral cyclopentadienyl ligands is reported, and their steric electronic parameters are mapped. application potential these complexes for asymmetric C-H functionalizations 3d-metals shown by the dihydroisoquinolones from N-chlorobenzamides broad range alkenes. transformation proceeds excellent enantioselectivities up to 99.5:0.5 er high regioselectivities. observed values outperform best rhodium(III)-based methods this reaction type. Moreover, challenging substrates such as alkyl alkenes also react regio- enantioselectivities.

Язык: Английский

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Iron- and cobalt-catalyzed C(sp³)–H bond functionalization reactions and their application in organic synthesis

Chemical Society Reviews, Год журнала: 2020, Номер 49(15), С. 5310 - 5358

Опубликована: Янв. 1, 2020

This review highlights the developments in iron and cobalt catalyzed C(sp³)–H bond functionalization reactions with emphasis on their applications organic synthesis, i.e. natural products pharmaceuticals synthesis and/or modification.

Язык: Английский

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Cobalt‐Catalyzed Annulation Reactions via C−H Bond Activation

ChemCatChem, Год журнала: 2017, Номер 10(4), С. 683 - 705

Опубликована: Ноя. 1, 2017

Abstract Considerable research attention has been directed towards the use of first‐row transition metals in organic synthesis. The more abundant, and less expensive cobalt is considered to be an effective alternative for second third‐row noble metals, especially C−H bond functionalization reactions. In this Minireview, we will summarize features, recent achievements Co‐catalyzed directing group assisted activation/cyclization reactions their mechanistic insights.

Язык: Английский

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Thioamide‐Directed Cobalt(III)‐Catalyzed Selective Amidation of C(sp³)−H Bonds

Angewandte Chemie International Edition, Год журнала: 2017, Номер 56(52), С. 16550 - 16554

Опубликована: Окт. 28, 2017

A mild, oxidant-free, and selective Cp*CoIII -catalyzed amidation of thioamides with robust dioxazolone amidating agents via C(sp3 )-H bond activation to generate the desired amidated products is reported. The method efficient allows for C-H a wide range functionalized aryl-, heteroaryl-, alkyl-substituted dioxazolones under conditions. observed regioselectivity towards primary supported by computational studies cyclometalation proposed proceed means an external carboxylate-assisted concerted metalation/deprotonation mechanism. reported rare example use directing group other than commonly used pyridine quinolone classes functionalization first exploit thioamides.

Язык: Английский

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Recent advances in cobalt-catalysed C–H functionalizations

Organic & Biomolecular Chemistry, Год журнала: 2019, Номер 17(48), С. 10119 - 10141

Опубликована: Янв. 1, 2019

Ready availability, low cost and toxicity of cobalt salts have redirected the attention researchers away from noble metals, such as Pd, Rh, Ir, towards Co in field C-H functionalization. In this context, examples Co-catalysed functionalization exponentially grown over last few decades. This present review focuses on most recent developments C(sp2)-H C(sp3)-H functionalizations. Included is also a comprehensive overview enantioselective transformations.

Язык: Английский

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Chiral 2-Aryl Ferrocene Carboxylic Acids for the Catalytic Asymmetric C(sp³)–H Activation of Thioamides

Organometallics, Год журнала: 2019, Номер 38(20), С. 3921 - 3926

Опубликована: Июль 29, 2019

Enantioselective C–H functionalization reactions using trivalent group 9 metals (Co, Rh, Ir) have been investigated mainly on the basis of development well-designed chiral cyclopentadienyl (Cp) ligands. Although it has recently demonstrated that carboxylic acids combined with achiral Cp-type ligands can enable highly enantioselective reactions, structural diversity applied remains limited. Here, we report 2-aryl ferrocene acids, which are easily obtained from diastereoselective ortho lithiation and Suzuki–Miyaura coupling, serve as external sources for Cp*CoIII-catalyzed C(sp3)–H amidation α-aryl thioamides dioxazolones.

Язык: Английский

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Recent Advances in [Cp*M^III] (M = Co, Rh, Ir)‐Catalyzed Intramolecular Annulation Through C–H Activation

European Journal of Organic Chemistry, Год журнала: 2018, Номер 2018(42), С. 5777 - 5794

Опубликована: Март 15, 2018

This review aims to summarize the recent advances in field of Cp*M III (Co, Rh, Ir)‐catalyzed C–H activation followed by subsequent intramolecular reaction. approach has allowed synthesis valuable heterocycles with high structural diversity and complexity, including polycyclic macrocyclic compounds. In this review, a particular attention been made nature coupling partner (alkene, alkyne, etc) its connection either aryl (or vinyl) group or directing group. Hence, different types transformation can occur, involving one two cyclizations depending on Finally, we discuss some mechanistical aspects (role external internal oxidation, account for formation cyclic structures.

Язык: Английский

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Cp*Co(III)-Catalyzed C–H Acylmethylation of Arenes by Employing Sulfoxonium Ylides as Carbene Precursors

Organic Letters, Год журнала: 2018, Номер 20(18), С. 5981 - 5984

Опубликована: Сен. 12, 2018

A Cp*Co(III)-catalyzed C-H bond functionalization of a range arenes by employing sulfoxonium ylides as carbene precursors instead diazo compounds and other has been established. This reaction is highly efficient without any additive, possesses high step atom economies, tolerates functional groups.

Язык: Английский

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