Organocatalytic Enantioselective Synthesis of Axially ChiralN,N′‐Bisindoles

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(15)

Опубликована: Фев. 7, 2023

This study establishes the first organocatalytic enantioselective synthesis of axially chiral N,N'-bisindoles via phosphoric acid-catalyzed formal (3+2) cycloadditions indole-based enaminones as novel platform molecules with 2,3-diketoesters, where de novo indole-ring formation is involved. Using this new strategy, various were synthesized in good yields and excellent enantioselectivities (up to 87 % yield 96 ee). More importantly, class exhibited some degree cytotoxicity toward cancer cells was derived into phosphine ligands high catalytic activity. provides a strategy for using asymmetric organocatalysis realize applications such scaffolds medicinal chemistry catalysis.

Язык: Английский

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Catalytic Asymmetric Synthesis of Axially Chiral Diaryl Ethers through Enantioselective Desymmetrization

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(14)

Опубликована: Фев. 10, 2023

Axially chiral diaryl ethers are a type of unique atropisomers bearing two potential axes, which have applications in variety research fields. However, the catalytic enantioselective synthesis these ether is largely underexplored when compared to asymmetric biaryl or other types atropisomers. Herein, we report highly efficient through an organocatalyzed desymmetrization protocol. The phosphoric acid-catalyzed electrophilic aromatic aminations symmetrical 1,3-benzenediamine substrates afforded series excellent yields and enantioselectivities. facile construction heterocycles by utilizations 1,2-benzenediamine moiety products provided access structurally diverse novel azaarene-containing

Язык: Английский

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Recent progress toward developing axial chirality bioactive compounds

European Journal of Medicinal Chemistry, Год журнала: 2022, Номер 243, С. 114700 - 114700

Опубликована: Авг. 28, 2022

Язык: Английский

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Asymmetric Synthesis of Remotely Chiral Naphthols and Naphthylamines via Naphthoquinone Methides

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(23), С. 12802 - 12811

Опубликована: Июнь 5, 2023

Quinone methides are well-established intermediates in asymmetric synthesis. In contrast, their extended analogues with the carbonyl and methide units distributed across two different rings have not been exploited Herein, we achieved first process involving such intermediates. Specifically, use of suitable chiral phosphoric acids enabled situ generation 2-naphthoquinone 8-methides corresponding aza counterparts for mild one-pot nucleophilic addition. These processes provided rapid access to a wide range previously less accessible remotely naphthols naphthylamines both high efficiency excellent enantioselectivity. Control experiment DFT calculations important insights into reaction mechanism, which likely involves acid molecules enantiodetermining transition states. This work serves as proof concept exploitation new types quinone versatile synthesis, thus providing platform efficient construction remote benzylic stereogenic centers aromatic compounds.

Язык: Английский

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Atroposelective Access to 1,3‐Oxazepine‐Containing Bridged Biaryls via Carbene‐Catalyzed Desymmetrization of Imines

Angewandte Chemie International Edition, Год журнала: 2022, Номер 62(1)

Опубликована: Сен. 10, 2022

Abstract We disclose herein an atroposelective synthesis of novel bridged biaryls containing medium‐sized rings via N‐heterocyclic carbene organocatalysis. The reaction starts with addition the catalyst to aminophenol‐derived aldimine substrate. Subsequent oxidation and intramolecular desymmetrization lead formation 1,3‐oxazepine‐containing in good yields excellent enantioselectivities. These biaryl products can be readily transformed into chiral phosphite ligands. Preliminary density function theory calculations suggest that origin enantioselectivity arises from more favorable frontier molecular orbital interactions transition state leading major product.

Язык: Английский

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Torsional Strain‐Independent Catalytic Enantioselective Synthesis of Biaryl Atropisomers

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(43)

Опубликована: Авг. 26, 2022

Catalytic asymmetric dynamic kinetic resolution of configurationally labile bridged biaryls is emerging as a powerful strategy for atropisomer synthesis. However, the reported examples suffer from an inherent challenge reactivity highly dependent on torsional strain biaryl substrates, which significantly narrows down scope and hampers application. Herein, we report our discovery development strain-independent reaction between thionolactones activated isocyanides. By employing auto-tandem silver catalysis, universal synthesis both tri- tetra-ortho-substituted thiazole-containing was realized in high yields with enantioselectivities. In addition, these products could be facilely converted to novel type bearing eight-membered lactone. Mechanistic studies were carried out elucidate cause this unusual reactivity.

Язык: Английский

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A Stereodivergent–Convergent Chiral Induction Mode in Atroposelective Access to Biaryls via Rhodium-Catalyzed C–H Bond Activation

ACS Catalysis, Год журнала: 2022, Номер 12(22), С. 13884 - 13896

Опубликована: Окт. 27, 2022

Understanding the reaction mechanisms, particularly chiral induction mode, is critical for development of new asymmetric catalytic reactions. Rhodium(III)-catalyzed C–H activation en route to atroposelective [4 + 2] annulative coupling with α-diazo β-ketoesters has been realized, affording axially phenanthrenes in good excellent enantioselectivity. A combination experimental and computational studies revealed a nontraditional stereodivergent–convergent mode. The proceeded rhodafluorene intermediate, followed by competitive, constructive, stereodivergent migratory insertions two Rh–C(aryl) bonds into carbene species give β-ketoester intermediates. Then, other bond migratorily inserts ketone carbonyl group. Following this stereodetermining insertion, an ester-chelated rhodium(III) alkoxide bearing poorly controlled centers well-controlled C(sp2)–C(sp3) axis generated. final product delivered via stereoconvergent elimination retention axial chirality loss central chirality.

Язык: Английский

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Recent Progress of Electron‐Withdrawing‐Group‐Tethered Arenes Involved Asymmetric Nucleophilic Aromatic Functionalizations

Advanced Synthesis & Catalysis, Год журнала: 2022, Номер 364(21), С. 3630 - 3650

Опубликована: Окт. 3, 2022

Abstract Electron‐withdrawing groups (EWG) have emerged as a powerful tool for the activation of various arenes to promote nucleophilic dearomative additions construction complicated chiral cyclic structures under asymmetric catalytic systems. Nitro‐indoles, nitro‐benzofurans/benzothiophenes, and related nitro‐heteroarenes are widely applied in reaction with nucleophiles construct enantioenriched polycyclic skeletons via dearomatization process. Meanwhile, electron‐deficient azo‐group nitroso‐group an alternative arenes, which enable formal aromatic arylations electrophilic aromatics novel biaryl atropisomers. Besides, azo‐naphthanenes served dipolar surrogates dipolarophiles proceed cycloadditions skeletons. The EWG‐tethered arene has proven be versatile protocol structurally diversified backbones. This review summarizes latest progress involved transformations organo‐ or transition metal catalysis. magnified image

Язык: Английский

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Catalytic Asymmetric Synthesis of Axially Chiral Diaryl Ethers through Enantioselective Desymmetrization

Angewandte Chemie, Год журнала: 2023, Номер 135(14)

Опубликована: Фев. 10, 2023

Abstract Axially chiral diaryl ethers are a type of unique atropisomers bearing two potential axes, which have applications in variety research fields. However, the catalytic enantioselective synthesis these ether is largely underexplored when compared to asymmetric biaryl or other types atropisomers. Herein, we report highly efficient through an organocatalyzed desymmetrization protocol. The phosphoric acid‐catalyzed electrophilic aromatic aminations symmetrical 1,3‐benzenediamine substrates afforded series excellent yields and enantioselectivities. facile construction heterocycles by utilizations 1,2‐benzenediamine moiety products provided access structurally diverse novel azaarene‐containing

Язык: Английский

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Recent advances in atroposelective synthesis of axially chiral heterobiaryl featuring indole frameworks

Tetrahedron, Год журнала: 2023, Номер 149, С. 133716 - 133716

Опубликована: Ноя. 3, 2023

Язык: Английский

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