Atroposelective Synthesis of Axially Chiral Styrenes via an Asymmetric C–H Functionalization Strategy

Chem, Год журнала: 2020, Номер 6(2), С. 497 - 511

Опубликована: Янв. 9, 2020

Язык: Английский

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Palladium‐Catalyzed Enantioselective Cacchi Reaction: Asymmetric Synthesis of Axially Chiral 2,3‐Disubstituted Indoles

Angewandte Chemie International Edition, Год журнала: 2019, Номер 59(5), С. 2105 - 2109

Опубликована: Ноя. 22, 2019

We report herein the first examples of a palladium-catalyzed enantioselective Cacchi reaction for synthesis indoles bearing chiral C2-aryl axis. In presence catalytic amount Pd(OAc)2 and (R,R)-QuinoxP* ligand, N-aryl(alkyl)sulfonyl-2-alkynylanilides with arylboronic acids under oxygen atmosphere afforded enantioenriched 2,3-disubstituted in high yields enantioselectivity. The indole ring is constructed de novo this process complexation-induced chirality transfer proposed to account observed

Язык: Английский

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Synthesis of Axially Chiral Styrenes through Pd‐Catalyzed Asymmetric C−H Olefination Enabled by an Amino Amide Transient Directing Group

Angewandte Chemie International Edition, Год журнала: 2020, Номер 59(16), С. 6576 - 6580

Опубликована: Фев. 3, 2020

Abstract The atroposelective synthesis of axially chiral styrenes remains a formidable challenge due to their relatively lower rotational barriers compared the biaryl atropoisomers. Herein, we describe construction through Pd II ‐catalyzed C−H olefination, using bulky amino amide as transient auxiliary. Various were produced with good yields and high enantioselectivity (up 95 % yield 99 ee ). Carboxylic acid derivatives resulting showed superior enantiocontrol over counterparts in Co III enantioselective C(sp 3 )−H amidation thioamide. Mechanistic studies suggest that cleavage is enantioselectivity‐determining step.

Язык: Английский

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Rhodium-Catalyzed Atroposelective Oxidative C–H/C–H Cross-Coupling Reaction of 1-Aryl Isoquinoline Derivatives with Electron-Rich Heteroarenes

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(37), С. 15678 - 15685

Опубликована: Авг. 31, 2020

Rhodium(III)-catalyzed enantioselective oxidative C–H/C–H cross-coupling reaction between two arenes is disclosed. With the combination of a chiral CpRh(III) complex and carboxylic acid additive, direct coupling reactions 1-aryl isoquinoline derivatives electron-rich heteroarenes such as thiophenes, furans, benzothiophenes, benzofurans are realized via double C–H functionalization process. A series axially compounds obtained in excellent yields enantioselectivities (up to 99% yield ee). Mechanistic studies suggest that both bond cleavages may not be turnover-limiting step.

Язык: Английский

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Atroposelective Phosphoric Acid Catalyzed Three‐Component Cascade Reaction: Enantioselective Synthesis of Axially Chiral N‐Arylindoles

Angewandte Chemie International Edition, Год журнала: 2019, Номер 58(44), С. 15824 - 15828

Опубликована: Авг. 28, 2019

An efficient organocatalytic atroposelective three-component cascade reaction of 2,3-diketoesters, aromatic amines, and 1,3-cyclohexanediones has been developed for the highly enantioselective synthesis axially chiral N-arylindoles. The success this method derives from use a newly second-generation spirocyclic phosphoric acid as catalyst. In addition, protocol was extended to an monophosphorus ligand.

Язык: Английский

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Divergent Synthesis of Tunable Cyclopentadienyl Ligands and Their Application in Rh-Catalyzed Enantioselective Synthesis of Isoindolinone

Journal of the American Chemical Society, Год журнала: 2020, Номер 142(16), С. 7379 - 7385

Опубликована: Апрель 7, 2020

A series of rhodium complexes bearing sterically and electronically tunable cyclopentadienyl ligands, prepared by utilizing Co2(CO)8-mediated [2+2+1] cyclization as a key step, were synthesized. In the presence 2.5 mol% CpmRh4, unprecedented enantioselective [4+1] annulation reaction benzamides alkenes was achieved with broad substrate scope under mild conditions, providing variety isoindolinones excellent regio- enantioselectivity (up to 94% yield, 97:3 er). Preliminary mechanistic studies suggest that involves an oxidative Heck intramolecular alkene hydroamination reaction.

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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Enantioselective Synthesis of Nitrogen–Nitrogen Biaryl Atropisomers via Copper-Catalyzed Friedel–Crafts Alkylation Reaction

Journal of the American Chemical Society, Год журнала: 2021, Номер 143(37), С. 15005 - 15010

Опубликована: Сен. 8, 2021

Nitrogen–nitrogen bonds containing motifs are ubiquitous in natural products and bioactive compounds. However, the atropisomerism arising from a restricted rotation around an N–N bond is largely overlooked. Here, we describe method to access first enantioselective synthesis of biaryl atropisomers via Cu-bisoxazoline-catalyzed Friedel–Crafts alkylation reaction. A wide range axially chiral bisazaheterocycle compounds were efficiently prepared high yields with excellent enantioselectivities desymmetrization kinetic resolution. Heating experiments showed that have rotational barriers.

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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