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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Design and catalytic atroposelective synthesis of axially chiral isochromenone-indoles

Science China Chemistry, Год журнала: 2022, Номер 65(10), С. 1929 - 1937

Опубликована: Сен. 13, 2022

Язык: Английский

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Pd-Catalyzed Asymmetric Larock Indole Synthesis to Access Axially Chiral N-Arylindoles

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(8), С. 5493 - 5501

Опубликована: Фев. 13, 2024

Larock indole synthesis is one of the most straightforward and efficient methods for indoles; however, there has been no asymmetric version yet construction indole-based axially chiral N-arylindoles since its initial report in 1991. Herein we first example an by employing a sulfinamide phosphine (SadPhos) ligand (Ming-Phos) with palladium. It allows rapid wide range N-arylindole compounds good yields up to 98:2 er. The application this unique scaffold as organocatalyst promising. Furthermore, kinetic study revealed that alkyne migratory insertion rate-determining step, which proven density functional theory (DFT) calculations. Additionally, DFT studies also suggest N–C dihedral difference caused steric hindrance contributes enantioselectivity control.

Язык: Английский

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Catalytic Asymmetric Diastereodivergent Synthesis of 2-Alkenylindoles Bearing both Axial and Central Chirality

Precision Chemistry, Год журнала: 2024, Номер 2(5), С. 208 - 220

Опубликована: Апрель 23, 2024

The catalytic asymmetric diastereodivergent synthesis of axially chiral 2-alkenylindoles was established via phosphoric acid-catalyzed addition reactions C3-unsubstituted with

Язык: Английский

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Atropisomeric Phosphine Ligands Bearing C–N Axial Chirality: Applications in Enantioselective Suzuki–Miyaura Cross-Coupling Towards the Assembly of Tetra-ortho-Substituted Biaryls

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(32), С. 14864 - 14873

Опубликована: Авг. 3, 2022

Biaryl phosphines bearing C(Ar)–C(Ar) axial chirality are commonly known and have been successfully applied in many asymmetric catalyses. Nevertheless, the development of a chiral ligand having an axially C(Ar)–N backbone remains elusive due to its undesirable less restricted rotational barrier. In fact, it is highly attractive overcome this challenge as incorporation N-donor component at axis more favorable toward transient metal coordination, thus, better outcome stereocommunication anticipated approaching substrates. Herein, we present rational design new collection featuring C–N their applications enantioselective Suzuki–Miyaura cross-coupling for accessing steric hindered tetra-ortho-substituted biaryls (26 examples up 98:2 er). It worth noting that embodied carbazolyl framework crucial succeed reaction, by fruitful relief bulky substrate coordination transmetalation via fleeting Pd–N jumping Pd-π fashion. DFT calculation reveals interesting Pd-arene-walking characteristic across plane attaining lower energy-preferred route catalytic cycle. The theoretical study predicts stereooutcome matches enantioselectivity with experimental results.

Язык: Английский

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Enantioselective Copper‐Catalyzed Formal [2+1] and [4+1] Annulations of Diynes with Ketones via Carbonyl Ylides

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

Опубликована: Авг. 17, 2022

Carbonyl ylides have proven to be powerful synthons for the efficient construction of various valuable O-heterocycles, and formation carbonyl by reaction metal carbenes with carbonyls has attracted increasing attention over past decades. However, a catalyst-controlled highly enantioselective from is extremely challenging. Herein, we report novel copper-catalyzed asymmetric formal [2+1] [4+1] annulations diynes ketones via ylides. Importantly, this protocol not only represents first example successful epoxidation ylides, but also constitutes vinyl cations compounds. This method leads divergent, practical atom-economical synthesis range chiral oxiranes dihydrofurans in moderate excellent yields generally enantioselectivities diastereoselectivities remote-stereocontrol strategy.

Язык: Английский

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Construction of Axially Chiral Indoles by Cycloaddition–Isomerization via Atroposelective Phosphoric Acid and Silver Sequential Catalysis

ACS Catalysis, Год журнала: 2022, Номер 12(13), С. 8094 - 8103

Опубликована: Июнь 22, 2022

Axially chiral indole-based frameworks occur in natural products, bioactive molecules, and ligands. Thus, the development of catalytic asymmetric atroposelective approaches for de novo construction these is highly valuable. Here, organo/metal combined dual catalysis strategy valuable axially indole has been developed. This protocol utilized a catalyst system two phosphoric acids (1 mol %) combination with AgNO3 was based on unreported intermolecular cycloaddition–isomerization reaction our recently introduced C-alkynyl N,O-acetals 2-naphthylamines. An important class hitherto inaccessible indoles C–N axis were obtained good yields enantioselectivities. The also provided platform catalyst-controlled synthesis bearing axes, which are difficult to access by existing methods. work an example 2-naphthylamines used as 1,3-dinucleophiles three-atom (CCN) synthons cycloadditions.

Язык: Английский

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Catalyst‐Dependent Stereospecific [3,3]‐Sigmatropic Rearrangement of Sulfoxide‐Ynamides: Divergent Synthesis of Chiral Medium‐Sized N,S‐Heterocycles

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(28)

Опубликована: Апрель 27, 2022

Medium-sized N,S-heterocycles have received tremendous interest due to their biological activities and potential medical applications. However, asymmetric synthesis of these compounds are extremely rare. Described herein is a catalyst-dependent [3,3]-sigmatropic rearrangement sulfoxide-ynamides, enabling divergent atom-economic series valuable medium-sized in moderate good yields with broad substrate scope. Importantly, excellent enantioselectivities been achieved via an unprecedented chirality-transfer. Moreover, theoretical calculations employed elucidate the origins stereospecific [3,3]-rearrangement.

Язык: Английский

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Construction of Axially Chiral Arylpyrroles via Atroposelective Diyne Cyclization

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(23)

Опубликована: Март 30, 2023

Axially chiral biaryls widely exist in natural products and pharmaceuticals are used as ligands catalysts asymmetric synthesis. Compared to the well-established axially 6-membered biaryl skeletons, examples of 5-membered have been quite scarce, mono-substituted 3-arylpyrrole atropisomers not reported. Here, we disclose a copper-catalyzed atroposelective diyne cyclization for construction range arylpyrrole good excellent yields with generally enantioselectivities via oxidation X-H insertion vinyl cations. Importantly, this protocol only represents first synthesis atropisomers, but also constitutes example atropisomer Theoretical calculations further support mechanism cation-involved elucidate origin enantioselectivity.

Язык: Английский

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Design and Catalytic Asymmetric Synthesis of Furan‐Indole Compounds Bearing both Axial and Central Chirality

Angewandte Chemie International Edition, Год журнала: 2023, Номер 63(8)

Опубликована: Дек. 29, 2023

Abstract In the chemistry community, catalytic asymmetric synthesis of furan‐based compounds bearing both axial and central chirality has proven to be a significant but challenging issue owing importance difficulty in constructing such frameworks. this work, we have realized first five‐five‐membered via organocatalytic (2+4) annulation achiral furan‐indoles with 2,3‐indolyldimethanols uncommon regioselectivity. By strategy, furan‐indole were synthesized high yields excellent regio‐, diastereo‐, enantioselectivities. Moreover, theoretical calculations conducted provide an in‐depth understanding reaction pathway, activation mode, origin selectivity.

Язык: Английский

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