Palladium/Norbornene Cooperative Catalysis

Chemical Reviews, Journal Year: 2019, Volume and Issue: 119(12), P. 7478 - 7528

Published: April 25, 2019

Palladium/norbornene cooperative catalysis has emerged as a distinct approach to construct polyfunctionalized arenes from readily available starting materials. This Review provides comprehensive overview of this field, including the early stoichiometric investigations, catalytic reaction developments, well applications in syntheses bioactive compounds and polymers. The section reactions is divided into two parts according initiation mode: Pd(0)-initiated Pd(II)-initiated reactions.

Language: Английский

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Toolbox for Distal C–H Bond Functionalizations in Organic Molecules

Chemical Reviews, Journal Year: 2021, Volume and Issue: 122(6), P. 5682 - 5841

Published: Oct. 18, 2021

Transition-metal-catalyzed C–H activation has developed a contemporary approach to the omnipresent area of retrosynthetic disconnection. Scientific researchers have been tempted take help this methodology plan their synthetic discourses. This paradigm shift helped in development industrial units as well, making synthesis natural products and pharmaceutical drugs step-economical. In vast zone bond activation, functionalization proximal bonds gained utmost popularity. Unlike bonds, distal is more strenuous requires distinctly specialized techniques. review, we compiled various methods adopted functionalize mechanistic insights within each these procedures, scope methodology. With give complete overview expeditious progress made field organic chemistry while also highlighting its pitfalls, thus leaving open for further modifications.

Language: Английский

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Dirhodium tetracarboxylates as catalysts for selective intermolecular C–H functionalization

Nature Reviews Chemistry, Journal Year: 2019, Volume and Issue: 3(6), P. 347 - 360

Published: May 7, 2019

Language: Английский

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Arene diversification through distal C(sp ² )−H functionalization

Science, Journal Year: 2021, Volume and Issue: 372(6543)

Published: May 13, 2021

Transition metal-catalyzed aryl C-H activation is a powerful synthetic tool as it offers step and atom-economical routes to site-selective functionalization. Compared with proximal ortho-C-H activation, distal (meta- and/or para-) remains more challenging due the inaccessibility of these sites in formation energetically favorable organometallic pretransition states. Directing catalyst toward bonds requires judicious template engineering design, well prudent choice ligands. This review aims summarize recent elegant discoveries exploiting directing group assistance, transient mediators or traceless directors, noncovalent interactions, ligand selection control activation.

Language: Английский

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Synthesis of Atropisomers by Transition-Metal-Catalyzed Asymmetric C–H Functionalization Reactions

Journal of the American Chemical Society, Journal Year: 2021, Volume and Issue: 143(35), P. 14025 - 14040

Published: Aug. 25, 2021

Transition-metal-catalyzed enantioselective C-H functionalization has become a powerful strategy for the formation of C-C or C-X bonds, enabling highly asymmetric synthesis wide range enantioenriched compounds. Atropisomers are widely found in natural products and pharmaceutically relevant molecules, have also applications as privileged frameworks chiral ligands catalysts. Thus, research into routes atropisomers garnered great interest recent years. In this regard, transition-metal-catalyzed emerged an atom-economic efficient toward their synthesis. Perspective, approaches by reactions summarized. The main focus here is on catalysis via Pd, Rh, Ir complexes, which been most frequently utilized catalysts among reported reactions. Finally, we discuss limitations available protocols give outlook possible future avenues research.

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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Strategic evolution in transition metal-catalyzed directed C–H bond activation and future directions

Coordination Chemistry Reviews, Journal Year: 2020, Volume and Issue: 431, P. 213683 - 213683

Published: Dec. 9, 2020

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 Cobalt(III)‐Catalyzed C−H Activation Enabled by Chiral Carboxylic Acid Cooperation

Angewandte Chemie International Edition, Journal Year: 2018, Volume and Issue: 57(47), P. 15425 - 15429

Published: Oct. 6, 2018

The enantioselective cobalt(III)-catalyzed C-H alkylation was achieved through the design of a novel chiral acid. activation characterized by high position-, regio- and enantio-control under exceedingly mild reaction conditions. Thereby, robust cooperative cobalt(III) catalysis proved tolerant valuable electrophilic functional groups, including hydroxyl, bromo, iodo substituents. Mechanistic studies revealed considerable additive effect on kinetics negative non-linear-effect.

Language: Английский

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Recent advances in the sulfonylation of C–H bonds with the insertion of sulfur dioxide

Chemical Communications, Journal Year: 2018, Volume and Issue: 54(89), P. 12561 - 12569

Published: Jan. 1, 2018

Recent advances in the sulfonylation of C-H bonds with insertion sulfur dioxide are summarized. Usually, a surrogate, DABCO·(SO2)2, is used, which avoids utilization gaseous transformation. Inorganic sulfites such as sodium metabisulfite also effective C(sp3)-H bond sulfonylation. under transition metal catalysis or through radical process has been developed. In some cases, can be performed catalyst- and additive-free conditions, facilitated by visible light irradiation. The efficiency investigated merging catalysis.

Language: Английский

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