Recent Advances in Catalytic Asymmetric Construction of Atropisomers

Chemical Reviews, Год журнала: 2021, Номер 121(8), С. 4805 - 4902

Опубликована: Март 27, 2021

Atropisomerism is a stereochemical behavior portrayed by three-dimensional molecules that bear rotationally restricted σ bond. Akin to the well-represented point-chiral molecules, atropisomerically chiral compounds are finding increasing utilities in many disciplines where molecular asymmetry influential. This provides steady demand on atroposelective synthesis, numerous synthetic pursuits have been rewarded with conceptually novel and streamlined methods while expanding structural diversity of atropisomers. review summarizes key achievements stereoselective preparation biaryl, heterobiaryl, nonbiaryl atropisomers documented between 2015 2020. Emphasis placed strategies for each class, examples cited illustrate potential applications accessed atropochiral targets.

Язык: Английский

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

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(35), С. 14025 - 14040

Опубликована: Авг. 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.

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2020, Номер 60(24), С. 13198 - 13224

Опубликована: Июль 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.

Язык: Английский

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

ACS Catalysis, Год журнала: 2020, Номер 10(23), С. 13748 - 13793

Опубликована: Ноя. 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.

Язык: Английский

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Organocatalytic Atroposelective Synthesis of N−N Axially Chiral Indoles and Pyrroles by De Novo Ring Formation

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(17)

Опубликована: Янв. 26, 2022

Abstract The first highly atroposelective construction of N−N axially chiral indole scaffolds was established via a new strategy de novo ring formation. This makes use the organocatalytic asymmetric Paal–Knorr reaction well‐designed N ‐aminoindoles with 1,4‐diketones, thus affording ‐pyrrolylindoles in high yields and excellent atroposelectivities (up to 98 % yield, 96 ee). In addition, this is applicable for synthesis bispyrroles 97 More importantly, such heterocycles can be converted into organocatalysts applications catalysis, some molecules display potent anticancer activity. work not only provides but also offers members atropisomer family promising synthetic medicinal chemistry.

Язык: Английский

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Rhodium-Catalyzed Asymmetric C–H Functionalization Reactions

Chemical Reviews, Год журнала: 2023, Номер 123(16), С. 10079 - 10134

Опубликована: Авг. 1, 2023

This review summarizes the advancements in rhodium-catalyzed asymmetric C–H functionalization reactions during last two decades. Parallel to rapidly developed palladium catalysis, rhodium catalysis has attracted extensive attention because of its unique reactivity and selectivity reactions. In recent years, Rh-catalyzed have been significantly many respects, including catalyst design, reaction development, mechanistic investigation, application synthesis complex functional molecules. presents an explicit outline catalysts ligands, mechanism, scope coupling reagents, applications.

Язык: Английский

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Catalytic Asymmetric Synthesis of Axially Chiral 3,3'‐Bisindoles by Direct Coupling of Indole Rings

Chinese Journal of Chemistry, Год журнала: 2022, Номер 40(18), С. 2151 - 2160

Опубликована: Май 31, 2022

Comprehensive Summary A new strategy for the enantioselective synthesis of axially chiral 3,3'‐bisindoles was devised by direct coupling two indole rings. This makes use C3‐umpolung reactivity 2‐indolylmethanols, which enables catalytic asymmetric addition reaction 2‐indolylmethanols with rationally designed 2‐substituted indoles, thus constructing 3,3'‐bisindole scaffolds in overall excellent yields (up to 98%) high enantioselectivities 96 : 4 er). approach not only has overcome challenges five‐five‐membered heterobiaryls, but also represents a application catalysis. More importantly, this class can undergo variety post‐functionalizations give 3,3'‐bisindole‐based organocatalysts, have found their preliminary applications

Язык: Английский

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Palladium-catalyzed asymmetric hydrophosphination of internal alkynes: Atroposelective access to phosphine-functionalized olefins

Chem, Год журнала: 2022, Номер 8(12), С. 3346 - 3362

Опубликована: Сен. 23, 2022

Язык: Английский

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The chemistry of heterocycles in the 21st century

Russian Chemical Reviews, Год журнала: 2024, Номер 93(7), С. RCR5125 - RCR5125

Опубликована: Июль 1, 2024

The chemistry of heterocyclic compounds has traditionally been and remains a bright area chemical science in Russia. This is due to the fact that many heterocycles find widest application. These are key structural fragments most drugs, plant protection agents. Many natural also derivatives heterocycles. At present, more than half hundreds millions known collective review devoted achievements Russian chemists this field over last 15–20 years. presents leading heterocyclists representing both RAS institutes university science. It worth noting wide scope review, terms geography author teams, covering whole our large country, diversity research areas. Practically all major types represented review. special attention focused on practical applications design new drugs biologically active compounds, high-energy molecules, materials for organic electronics photovoltaics, ligands coordination chemistry, other rapidly developing advances would not be possible without development fundamental transformations chemistry.<br> Bibliography — 2237 references.

Язык: Английский

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Rhodium‐Catalyzed Atroposelective Construction of Indoles via C−H Bond Activation

Angewandte Chemie International Edition, Год журнала: 2020, Номер 60(15), С. 8391 - 8395

Опубликована: Дек. 18, 2020

Reported herein is the rhodium(III)-catalyzed C-H activation of anilines bearing an N-isoquinolyl directing group for oxidative [3+2] annulation with four classes internal alkynes, leading to atroposelective indole synthesis via dynamic kinetic C-N reductive elimination constituting stereo-determining step. This reaction proceeds under mild conditions high regio- and enantioselectivity functional compatibility.

Язык: Английский

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