Enantioselective C−H Activation with Earth‐Abundant 3d Transition Metals

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(37), P. 12803 - 12818

Published: May 11, 2019

Molecular syntheses largely rely on time- and labour-intensive prefunctionalization strategies. In contrast, C-H activation represents an increasingly powerful approach that avoids lengthy of prefunctionalized substrates, with great potential for drug discovery, the pharmaceutical industry, material sciences, crop protection, among others. The enantioselective functionalization omnipresent bonds has emerged as a transformative tool step- atom-economical generation chiral molecular complexity. However, this rapidly growing research area remains dominated by noble transition metals, prominently featuring toxic palladium, iridium rhodium catalysts. Indeed, despite significant achievements, use inexpensive sustainable 3d metals in asymmetric activations is still clearly its infancy. Herein, we discuss remarkable recent progress transformations via organometallic base up to April 2019.

Language: Английский

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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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Enantioselective remote C–H activation directed by a chiral cation

Science, Journal Year: 2020, Volume and Issue: 367(6483), P. 1246 - 1251

Published: March 12, 2020

Chiral cations have been used extensively as organocatalysts, but their application to rendering transition metal-catalyzed processes enantioselective remains rare. This is despite the success of analogous charge-inverted strategy in which cationic metal complexes are paired with chiral anions. We report here a render common bipyridine ligand anionic and pair its iridium cation derived from quinine. applied these ion-paired long-range asymmetric induction desymmetrization geminal diaryl motif, located on carbon or phosphorus center, by C-H borylation. In principle, numerous classes could likewise be amenable this approach.

Language: Английский

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Chiral Cyclopentadienyl Ligands: Design, Syntheses, and Applications in Asymmetric Catalysis

Angewandte Chemie International Edition, Journal Year: 2020, Volume and Issue: 60(24), P. 13198 - 13224

Published: July 16, 2020

The creation of new chiral ligands capable providing high stereocontrol in metal-catalyzed reactions is crucial modern organic synthesis. production bioactive molecules as single enantiomers increasingly required, and asymmetric catalysis with metal complexes constitutes one the most efficient synthetic strategies to access optically active compounds. Herein we offer a historical overview on development derivatives ubiquitous cyclopentadienyl ligand (CpX ), detail their successful application broad range transformations. Those include functionalization challenging C-H bonds beyond, giving an extensive catalogue valuable molecules. A critical comparison existing families, design, synthesis, complexation different metals also provided. In addition, future research directions are discussed further enhance performance CpX enantioselective catalysis.

Language: Английский

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Transition Metal Catalyzed Enantioselective C(sp²)–H Bond Functionalization

ACS Catalysis, Journal Year: 2020, Volume and Issue: 10(23), P. 13748 - 13793

Published: Nov. 12, 2020

Direct catalytic transformation of C–H bonds to new functionalities has provided a powerful strategy synthesize complex molecular scaffolds in straightforward way. Unstinting efforts the synthetic community have helped overcome long-standing major challenge regioselectivity by introducing directing group concept. However, full potential cannot be realized unless activated are stereochemically controlled. The enantioselective bond functionalization could provide an imperative tool for sustainable way synthesizing chiral scaffolds. Despite intrinsic challenges achieving stereocontrol, developed different tools order achieve stereoselective functionalization. In this review, we discuss remarkable recent advances emerging area C(sp2)–H highlight and opportunities, emphasizing techniques so far.

Language: Английский

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Enantioselective C H Bond Functionalizations by 3d Transition-Metal Catalysts

Trends in Chemistry, Journal Year: 2019, Volume and Issue: 1(5), P. 471 - 484

Published: April 20, 2019

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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Enantioselective Synthesis of Chiral‐at‐Sulfur 1,2‐Benzothiazines by Cp^xRh^III‐Catalyzed C−H Functionalization of Sulfoximines

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(47), P. 15539 - 15543

Published: Oct. 10, 2018

Abstract Sulfoximines with stereogenic sulfur atoms are attractive structural motifs in drug discovery. A direct catalytic enantioselective method for the synthesis of sulfur‐chiral 1,2‐benzothiazines from readily accessible diaryl sulfoximines is presented. Rhodium(III) complexes equipped chiral cyclopentadienyl ligands and paired suitable carboxylic acid additives engage an enantiodetermining C−H activation directed by sulfoximine group. Subsequent trapping rhodacycle a broad range diazoketones gives access to S‐chiral synthetically highly substitution patterns good yields enantioselectivities.

Language: Английский

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Cp*Co(III)/MPAA-Catalyzed Enantioselective Amidation of Ferrocenes Directed by Thioamides under Mild Conditions

Organic Letters, Journal Year: 2019, Volume and Issue: 21(6), P. 1895 - 1899

Published: March 6, 2019

Cp*Cobalt(III)-catalyzed enantioselective C-H amidation of ferrocenes using monoprotected amino acids (MPAAs) as chiral ligands was developed. The reaction performed under mild conditions in high yields (up to 97%) with moderate enantioselectivity 77.5:22.5 er), providing a promising strategy create planar chirality via base-metal-catalyzed activation.

Language: Английский

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Efficient Synthesis of Sulfur-Stereogenic Sulfoximines via Ru(II)-Catalyzed Enantioselective C–H Functionalization Enabled by Chiral Carboxylic Acid

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(18), P. 6810 - 6816

Published: April 28, 2021

Ru(II)-catalyzed enantioselective C-H functionalization involving an enantiodetermining cleavage step remains undeveloped. Here we describe a activation/annulation of sulfoximines with α-carbonyl sulfoxonium ylides using novel class chiral binaphthyl monocarboxylic acids as ligands, which can be easily and modularly prepared from 1,1'-binaphthyl-2,2'-dicarboxylic acid. A broad range sulfur-stereogenic were in high yields excellent enantioselectivities (up to 99% yield ee) via desymmetrization, kinetic resolution, parallel resolution. Furthermore, the resolution products transformed sulfoxides key intermediates for kinase inhibitors.

Language: Английский

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