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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Atroposelective catalysis

Nature Reviews Chemistry, Год журнала: 2024, Номер 8(7), С. 497 - 517

Опубликована: Июнь 18, 2024

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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Organocatalytic Nazarov-type cyclization of 3-alkynyl-2-indolylmethanols: construction of axially chiral cyclopenta[b]indole scaffolds

Chemical Synthesis, Год журнала: 2023, Номер 3(1), С. 6 - 6

Опубликована: Янв. 1, 2023

In recent years, it has become an urgent task to design new types of indole-based platform molecules for Nazarov-type cyclizations and develop organocatalytic synthesizing indole derivatives. To fulfill this task, in work, by changing the alkynyl terminal substituent from t-Bu aryl group, reactivity 3-alkynyl-2-indolylmethanols is modulated serve as competent substrates Brønsted acid-catalyzed cyclization. Based on reactivity, first cyclization aryl-substituted with 2-naphthols accomplished, leading efficient construction a class axially chiral 3, 4-dihydrocyclopenta[b]indole scaffolds. This preliminary investigation asymmetric provides optional strategy atroposelective cyclopenta[b]indole addition, preparation optical purity established through resolution, which could complementary method catalytic approaches.

Язык: Английский

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Rhodium-Catalyzed N-Arylation of 2-Pyridones Enabled by 1,6-Acyl Migratory Rearrangement of 2-Oxypyridines

Organic Letters, Год журнала: 2023, Номер 25(11), С. 1974 - 1977

Опубликована: Март 15, 2023

An efficient rhodium-catalyzed dearomative rearrangement of 2-oxypyridines with quinone diazides has been developed for the direct synthesis N-arylated pyridones, in which a novel 1,6-O-to-O rather than 1,4-O-to-C acyl achieved under mild reaction conditions.

Язык: Английский

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Catalytic Enantioselective Synthesis of Boron‐Stereogenic and Axially Chiral BODIPYs via Rhodium(II)‐Catalyzed C‐H (Hetero)Arylation with Diazonaphthoquinones and Diazoindenines

Angewandte Chemie International Edition, Год журнала: 2024, Номер unknown

Опубликована: Окт. 29, 2024

The molecular engineering of boron dipyrromethenes (BODIPYs) has garnered widespread attention due to their structural diversity enabling tailored physicochemical properties for optimal applications. However, catalytic enantioselective synthesis structurally diverse boron-stereogenic BODIPYs through intermolecular desymmetrization and with atroposelectivity remains elusive. Here, we showcase rhodium(II)-catalyzed site-specific C-H (hetero)arylations prochiral polysubstituted diazonaphthoquinonesand diazoindenines, providing efficient pathways the rapid assembly versatile (hetero)arylated axially chiral long-range axial rotational restriction modes. synthetic application procedures been emphasized by BODIPY derivatives various functions. Photophysical properties, bioimaging, lipid droplet-specific targeting capability are also demonstrated, indicating promising applications in biomedical research, medicinal chemistry, material science.

Язык: Английский

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Atroposelective Synthesis of N–N Axially Chiral Bipyrroles via Rhodium-Catalyzed C–H Insertion Reaction

Organic Letters, Год журнала: 2023, Номер 25(26), С. 4808 - 4812

Опубликована: Июнь 27, 2023

An atroposelective synthesis of bipyrroles with an axially chiral N-N bond has been established via a rhodium-catalyzed C-H insertion reaction to provide the desired atropisomers in good yields (up 97% yield) excellent enantioselectivities 99% ee).

Язык: Английский

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Rh(II)-Catalyzed Synthesis of N-Aryl 2-pyridone Using 2-Oxypyridine and Diazonaphthoquinone Via 1,6-Benzoyl Migratory Rearrangement

Organic Letters, Год журнала: 2023, Номер 25(16), С. 2873 - 2877

Опубликована: Апрель 13, 2023

A Rh(II)-catalyzed simple and efficient synthesis of N-arylated 2-pyridone derivatives is described using 2-oxypyridine diazonaphthoquinone as coupling partners. The reaction proceeds through the insertion nitrogen atom derivative into quinoid carbene subsequent 1,6-benzoyl migratory rearrangement. broadened with sufficient scope has potential to offer axially chiral under suitable asymmetric conditions.

Язык: Английский

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Intermolecular Buchwald–Hartwig Reactions for Enantioselective Synthesis of Diverse Atropisomers: Rerouting the C–N Forming Mechanism to Substrate Oxygen-Assisted Reductive Elimination

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(24), С. 16567 - 16580

Опубликована: Июнь 7, 2024

Axially chiral biaryls featuring a C–N axis are important functional molecules in diverse fields. The asymmetric Buchwald–Hartwig reaction represents powerful strategy for these targets. Previous studies, however, have been predominantly restricted to intramolecular atroposelective coupling, likely due the steric and entropic effects reductive elimination of Pd(II) species with sterically congested aryl nitrogen groups. We now report two intermolecular coupling systems bulky NH lactams halohydrocarbons enabled by rerouting mechanism one that accommodates challenging substrates. Both exhibited group tolerance, excellent enantioselectivity, high Z selectivity (if applicable), affording atropisomeric biaryl olefins through de novo construction axis. Experimental computational studies were performed elucidate mechanism, switch pathways is traced effect (ortho substituent) halide substrate. A 2,6-disubstituted reorients proximal lactamide ligand its unusual O-ligation mode. With amide oxygen participation, this intermediate undergoes an accessible barrier five-membered ring transition state, pathway as well induction mode has much underexplored catalysis.

Язык: Английский

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Organocatalytic enantioselective synthesis of C_sp2–N atropisomers via formal C_sp2–O bond amination

Chemical Science, Год журнала: 2024, Номер 15(11), С. 3893 - 3900

Опубликована: Янв. 1, 2024

An organocatalyzed asymmetric synthesis of C sp2 –N atropisomers by formal –O amination has been established from 3-alkynyl-3-hydroxyisoindolinones and 1-methylnaphthalen-2-ols.

Язык: Английский

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