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

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 58(4), P. 1153 - 1157

Published: Nov. 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.

Language: Английский

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

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 26(33), P. 7346 - 7357

Published: Jan. 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

Language: Английский

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Peptide macrocyclization by transition metal catalysis

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(7), P. 2039 - 2059

Published: Jan. 1, 2020

Peptide macrocyclization continues expanding with the development of novel transition metal-catalyzed reactions capable both introducing conformational constraints and generating diversity at ring-closing moiety.

Language: Английский

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Ruthenium-Catalyzed Enantioselective C–H Functionalization: A Practical Access to Optically Active Indoline Derivatives

Journal of the American Chemical Society, Journal Year: 2019, Volume and Issue: 141(40), P. 15730 - 15736

Published: Sept. 19, 2019

Ru(II)-catalyzed enantioselective C–H activation/hydroarylation has been developed for the first time, allowing highly synthesis of indoline derivatives via catalytic activation. Commercially available Ru(II) arene complexes and chiral α-methylamines were employed as catalysts. Based on a sterically rigidified transient directing group, multisubstituted indolines produced in up to 92% yield with 96% ee. Further transformation resulting 4-formylindoline enables access an optically active tricyclic compound that is potential biological pharmaceutical interest.

Language: Английский

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Ruthenium(II)‐Catalyzed Asymmetric Inert C−H Bond Activation Assisted by a Chiral Transient Directing Group

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 59(9), P. 3475 - 3479

Published: Dec. 23, 2019

Abstract A ruthenium(II)‐catalyzed asymmetric intramolecular hydroarylation assisted by a chiral transient directing group has been developed. series of 2,3‐dihydrobenzofurans bearing all‐carbon quaternary stereocenters have prepared in remarkably high yields (up to 98 %) and enantioselectivities >99 % ee ). By this methodology, novel total synthesis CB2 receptor agonist MDA7 successfully

Language: Английский

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Recent advances in Rh(iii)/Ir(iii)-catalyzed C–H functionalization/annulation via carbene migratory insertion

Organic & Biomolecular Chemistry, Journal Year: 2021, Volume and Issue: 19(7), P. 1438 - 1458

Published: Jan. 1, 2021

The review highlighted diverse annulations, including nitrogen, oxygen, sulfur heterocycles and carbocylizations via Rh(iii)/Ir(iii)-catalyzed C–H functionalization/annulation with various arene carbene precursors.

Language: Английский

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Transition Metal‐Catalyzed Intermolecular Cascade C−H Activation/Annulation Processes for the Synthesis of Polycycles

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 27(1), P. 121 - 144

Published: June 12, 2020

Abstract Polycycles are abundantly present in numerous advanced chemicals, functional materials, bioactive molecules and natural products. However, the strategies for synthesis of polycycles limited to classical reactions transition metal‐catalyzed cross‐coupling reactions, requiring pre‐functionalized starting materials lengthy synthetic operations. The emergence novel approaches shows great promise fields organic/medicinal/materials chemistry. Among them, C−H activation followed by intermolecular annulation prevail, due their straightforward manner with high atom‐ step‐economy, providing rapid, concise efficient methods construction diverse polycycles. Several have been developed polycycles, relying on sequential multiple activation/annulation, or combination activation/annulation further interaction a proximal group, merger cycloaddition reaction, situ formation directing group. These attractive, efficient, step‐ atom‐economic from commercially available materials. This Minireview will provide an introduction helping researchers discover indirect connections reveal hidden opportunities. It also promote discovery activation.

Language: Английский

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Applications of Chiral Cyclopentadienyl (Cp^x) Metal Complexes in Asymmetric Catalysis

European Journal of Organic Chemistry, Journal Year: 2020, Volume and Issue: 2020(42), P. 6512 - 6524

Published: July 21, 2020

Metal complexes containing cyclopentadienyl (Cp) ligands are versatile and robust catalysts widely applied in organic synthesis. During the last two decades chiral Cp x have been a variety of enantioselective transformations. Often associated with Group 9 metals (Co, Rh, Ir), also used combination early transition‐metals rare‐earth elements. In this minireview asymmetric reactions that successfully steered ligand metal discussed according to coordinated. Several designs diverse array reactions, particular C–H functionalisation, binaphthyl‐derived leading field. Challenges these derive from need for their multi‐step synthesis, recently new were designed, which can be accessed shorter sequences readily available starting materials.

Language: Английский

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Transition Metal Promoted Cascade Heterocycle Synthesis through C−H Functionalization

Chemistry - A European Journal, Journal Year: 2020, Volume and Issue: 26(44), P. 9749 - 9783

Published: June 18, 2020

Sequential, domino and tandem reactions could be defined as a sequence of synthetic transformations that occur one after the other, in same reaction flask. This Review highlights recent advances at overlap two worlds: transition-metal mediated C-H activation trigger cascade reaction, for heterocycles synthesis. To shed some light on this intricate "middle-earth", focus was put mechanism rather than type metal or chronological order reaction. The aim is to separate, then highlight, true initiated by activation, compared other examples functionalization heterocycle syntheses.

Language: Английский

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Dual-Ligand-Enabled Ir(III)-Catalyzed Enantioselective C–H Amidation for the Synthesis of Chiral Sulfoxides

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(13), P. 7207 - 7215

Published: June 15, 2020

A rational designed Ir(III)-catalyzed enantioselective C–H amidation of dibenzyl sulfoxides through desymmetrization and parallel kinetic resolution is demonstrated. An Ir(III) complex equipped with a t-butyl cyclopentadienyl ligand paired modified chiral proline enables the highly sulfoxide-steered bond activation, providing an efficient straightforward way to construct sulfur centers. wide range dioxazolones are compatible this process, giving access variety functionalized sulfoxide compounds synthetically attractive amide substitution groups in good yields enantioselectivities. Moreover, flexible derivatization amidated was elaborated, various types scaffolds that would be potentially useful asymmetric catalysis as bidentate tridentate ligands.

Language: Английский

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