Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes

Chemical Communications, Год журнала: 2023, Номер 59(85), С. 12669 - 12684

Опубликована: Янв. 1, 2023

Recent advances in the asymmetric synthesis of axially chiral styrenes catalyzed by transition metals were summarized.

Язык: Английский

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Synthesis of Axially Chiral Biaryls through Cobalt(II)‐Catalyzed Atroposelective C−H Arylation

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(40)

Опубликована: Авг. 16, 2023

Highly efficient synthesis of axially chiral biaryl amines through cobalt-catalyzed atroposelective C-H arylation using easily accessible cobalt(II) salt and salicyloxazoline ligand has been reported. This methodology provides a straightforward sustainable access to broad range enantioenriched biaryl-2-amines in good yields (up 99 %) with excellent enantioselectivities % ee). The synthetic utility the unprecedented method is highlighted by its scalability diverse transformations.

Язык: Английский

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Atroposelective Three‐Component Coupling of Cyclic Diaryliodoniums and Sodium Cyanate Enabled by the Dual‐Role of Phenol

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(21)

Опубликована: Март 22, 2023

A copper-catalyzed atroposelective ring-opening reaction of cyclic diaryliodoniums, sodium cyanate (NaOCN) and phenols is reported. The chemoselectively affords axially chiral carbamates by sequential coupling diaryliodonium NaOCN, followed phenol. Mechanistic investigations revealed that phenol not only a reagent to trap highly active intermediate isocyanates, but it also activates the copper catalyst as standby ligand. were readily transformed into functionalized urea derivatives within simple nucleophilic substitution reaction.

Язык: Английский

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Chiral Cp^xRhodium(III)‐Catalyzed Enantioselective Aziridination of Unactivated Terminal Alkenes

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(12)

Опубликована: Янв. 27, 2024

Chiral cyclopentadienyl-rhodium(III) Cp

Язык: Английский

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Atroposelective Synthesis of Axially Chiral Diaryl Ethers by N-Heterocyclic-Carbene-Catalyzed Sequentially Desymmetric/Kinetic Resolution Process

The Journal of Organic Chemistry, Год журнала: 2024, Номер 89(6), С. 4067 - 4073

Опубликована: Фев. 23, 2024

We describe herein an N-heterocyclic-carbene-catalyzed atroposelective synthesis of axially chiral diaryl ethers. Through a sequentially enantioselective desymmetric process and kinetic resolution process, the products could be constructed in good yields with excellent enantiopurities. Both alcohols phenols were compatible this catalytic system. The carboxylic acids derived from esters proven to potential ligands for asymmetric synthesis, example, Rh(III)-catalyzed C–H functionalization.

Язык: Английский

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Organocatalytic Atroposelective Hydroselenation of Alkynes To Access Axially Chiral Vinyl Selenides

ACS Catalysis, Год журнала: 2025, Номер unknown, С. 4051 - 4060

Опубликована: Фев. 20, 2025

Язык: Английский

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Atroposelective Synthesis of Pyridoindolones Bearing Two Remote Distinct C–N Axes through Cobalt-Catalyzed Enantioselective C–H Activation

Journal of the American Chemical Society, Год журнала: 2025, Номер unknown

Опубликована: Март 13, 2025

C–N axially chiral compounds represent an important class of atropisomers that are prevalent in bioactive and material molecules. Despite recent advances synthetic methodologies, the asymmetric construction featuring multiple axes has been rarely explored, significantly limiting their further applications. Herein, we report a novel atroposelective synthesis diaxially pyridoindolones both six–five six–six through cobalt-catalyzed C–H annulation. This approach demonstrates exceptional efficiency, yielding diverse array with excellent yields atroposelectivities (60 examples, up to >99% yield, ee, >20:1 dr). Mechanistic studies revealed stereochemistry were generated fixed simultaneously during cyclometalation step, along unexpected amplification effect. The practicality this protocol is underscored by successful gram-scale syntheses various transformations, including formation phosphine ligand. Notably, photoluminescence quantum (ΦF 0.99) positive solvatochromism observed, coupled significant chiroptical properties, underscoring potential applications these organic fluorescent materials.

Язык: Английский

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Atroposelective Synthesis of Axially Chiral Styrenes by Platinum‐ Catalyzed Stereoselective Hydrosilylation of Internal Alkynes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(30)

Опубликована: Май 25, 2023

Abstract Hydrofunctionalization of alkynes is one the most efficient ways to access axially chiral styrenes with open‐chained olefins. While great advances have been achieved for 1‐alkynylnaphthalen‐2‐ols and analogues, atroposelective hydrofunctionalization unactivated internal lags. Herein we reported a platinum‐catalyzed hydrosilylation first time. With monodentate TADDOL‐derived phosphonite L1 used as ligand, various were in excellent enantioselectivities high E ‐selectivities. Control experiments showed that N H‐arylamide groups significant effects on both yields could act directing groups. The potential utilities products shown by transformations amide motifs products.

Язык: Английский

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Force-Triggered Atropisomerization of a Parallel Diarylethene to Its Antiparallel Diastereomers

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(29), С. 15668 - 15673

Опубликована: Июль 6, 2023

This paper describes a mechanical approach to inducing the atropisomerization of parallel diarylethene into its antiparallel diastereomers exhibiting distinct chemical reactivity. A congested mechanophore in (Ra,Sa)-configuration with mirror symmetry is atropisomerized C2 under ultrasound-induced force field. The resulting stereochemistry-converted material gains symmetry-allowed reactivity toward conrotatory photocyclization.

Язык: Английский

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2,2′‐Tethered Binaphthyl‐Embedded One‐Handed Helical Ladder Polymers: Impact of the Tether Length on Helical Geometry and Chiroptical Property

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(10)

Опубликована: Янв. 23, 2024

Synthetic breakthroughs diversify the molecules and polymers available to chemists. We now report first successful synthesis of a series optically-pure 2,2'-tethered binaphthyl-embedded helical ladder based on quantitative chemoselective ladderization by modified alkyne benzannulations using 4-alkoxy-2,6-dimethylphenylethynyl group as source, inaccessible conventional approach lacking 2,6-dimethyl substituents. Due defect-free helix formation, circular dichroism signal increased more than 6 times previously reported value. The resulting secondary structure can be fine-tuned controlling binaphthyl dihedral angle in repeating unit with variations 2,2'-alkylenedioxy tethering groups one carbon atom at time. optimization structures led strong circularly polarized luminescence high fluorescence quantum yield (28 %) dissymmetry factor (2.6×10

Язык: Английский

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