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 Alkene Atropisomers with Multiple Stereogenic Elements via Catalytic Asymmetric Rearrangement of 3‐Indolylmethanols

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

Опубликована: Июль 23, 2024

Abstract Catalytic enantioselective preparation of alkene atropisomers with multiple stereogenic elements and discovery their applications have become significant but challenging issues in the scientific community due to unique structures this class atropisomers. We herein report first catalytic atroposelective cyclopentenyl[ b ]indoles, a new kind atropisomers, point axial chirality via an unusual rearrangement reaction 3‐indolylmethanols under asymmetric organocatalysis. Notably, novel type promising developing chiral ligands or organocatalysts, discovering antitumor drug candidates fluorescence imaging materials. Moreover, theoretical calculations elucidated possible mechanism non‐covalent interactions control enantioselectivity. This approach offers synthetic strategy for elements, represents 3‐indolylmethanols, which will advance chemistry indole chemistry.

Язык: Английский

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Asymmetric Sulfonylation from a Reaction of Cyclopropan-1-ol, Sulfur Dioxide, and 1-(Alkynyl)naphthalen-2-ol

Organic Letters, Год журнала: 2024, Номер 26(15), С. 3321 - 3325

Опубликована: Апрель 10, 2024

Asymmetric sulfonylation from a reaction of cyclopropan-1-ol, sulfur dioxide, and 1-(alkynyl)naphthalen-2-ol in the presence catalytic amount organocatalyst at room temperature is developed. Axially chiral (S)-(E)-1-(1-(alkylsulfonyl)-2-arylvinyl)naphthalen-2-ols are generated moderate to good yields with excellent enantioselectivity regioselectivity under mild conditions. During this transformation, γ-keto sulfinate situ cyclopropan-1-ol dioxide acts as key intermediate.

Язык: Английский

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Copper- and Palladium-Cocatalyzed Chemo-, Regio-, Stereo-, and Atroposelective Arylboration of 1,3-Enynes

ACS Catalysis, Год журнала: 2024, Номер 14(15), С. 11318 - 11331

Опубликована: Июль 15, 2024

Catalytic enantioselective borylation reactions of unsaturated bonds as powerful tools for the synthesis diverse chiral organoboron compounds have gained much attention and wide applications in various fields. However, atroposelective arylboration reaction with carbon–carbon triple 1,3-enynes to obtain axially 1,3-dienylboronates remains an elusive significant challenge. Hence, we develop a cooperative copper- palladium-catalyzed assemble plentiful function enriched single step from easily available 1,3-enynes, B2pin2, aryl bromides high levels chemo-, regio-, stereo-, atroposelectivity. The mild conditions lead good functional group tolerance, which is proven by broad substrate scope late-stage functionalizations bioactive or drug molecules. Moreover, can be scaled up, series further transformations achieved. It worth emphasizing that several olefin catalysts ligands axial chirality also synthesized through corresponding elaborations such products, explains transformative ability application potential 1,3-dienylboronates. mechanism experiment density theory (DFT) calculations revealed process copper palladium catalysis, indicating chemoselectivity regioselectivity boration are determined enyne insertion on copper, atroposelectivity controlled reductive elimination center. Meanwhile, calculation demonstrated distinct interactions between P═O C═O groups Pd Bpin center key transition state formation products varying configurations while employing identical configuration ligands.

Язык: Английский

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Organocatalytic Activation of Alkynes Enabled Remote Control of Atroposelectivity via Vinylidene para-Quinone Methides

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

Опубликована: Янв. 15, 2025

Axially chiral o-VQMs have been extensively investigated as key intermediates to approach miscellaneous structures. By sharp contrast, their structural isomers p-VQMs not previously documented. The major reason, which results in the significant delay, may ascribe inherent challenges enantioselective activation of alkynes a remote manner. Herein, we demonstrate that mechanism para-hydroxyl-substituted arylacetylenes enables stereochemical induction, resulting axially aryl-alkenes with excellent enantiopurities. A series control experiments are performed elucidate insights this asymmetric transformation and verify involvement multimolecular CPAs reaction process. These findings expected unlock new feature for VQM chemistry inspire investigation into organocatalytic stereoselectivity.

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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Enantioselective organocatalytic synthesis of axially chiral aldehyde-containing styrenes via SNAr reaction-guided dynamic kinetic resolution

Nature Communications, Год журнала: 2023, Номер 14(1)

Опубликована: Авг. 19, 2023

The precise and efficient construction of axially chiral scaffolds, particularly toward the aryl-alkene atropoisomers with impeccably full enantiocontrol highly structural diversity, remains greatly challenging. Herein, we disclose an organocatalytic asymmetric nucleophilic aromatic substitution (SNAr) reaction aldehyde-substituted styrenes involving a dynamic kinetic resolution process via hemiacetal intermediate, offering novel facile way to significant axial styrene scaffolds. Upon treatment aldehyde-containing bearing (o-hydroxyl)aryl unit commonly available fluoroarenes in presence peptide-phosphonium salts, SNAr exquisite bridged biaryl lactol intermediate undergoes smoothly furnish series decorated various functionalities bioactive fragments high stereoselectivities (up >99% ee) complete E/Z selectivities. These resulting motifs are important building blocks for preparation diverse functionalized styrenes, which have great potential as privileged ligands/catalysts synthesis.

Язык: Английский

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Axially chiral styrene-based organocatalysts and their application in asymmetric cascade Michael/cyclization reaction

Chemical Science, Год журнала: 2023, Номер 14(35), С. 9496 - 9502

Опубликована: Янв. 1, 2023

An axially chiral styrene-based organocatalyst, featuring a combination of structure and pyrrole ring, has been designed synthesized. This catalyst demonstrates remarkable capabilities in producing wide range densely substituted spirooxindoles that feature an alkyne-substituted quaternary stereogenic center. These are generated through mild cascade Michael/cyclization reactions, resulting high conversion rates exceptional enantioselectivity. Our catalytic model, based on experiments, X-ray analysis DFT calculations suggests matched π-π interactions multiple H-bonds between the organocatalyst substrates play significant roles controlling stereoselectivity reaction.

Язык: Английский

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Enantioselective Aminative Dearomatization of Indoles via Electrophilic 1,6-Addition of p-Quinone Diimides (p-QDIs)

Organic Letters, Год журнала: 2024, Номер 26(23), С. 4932 - 4937

Опубликована: Июнь 3, 2024

Herein we report the first use of p-quinone diimide for aminative dearomatization 2,3-disubstituted indoles to furnish C3 aza-quaternary chiral indolenines. This approach, which proceeds via an electrophilic 1,6-addition diimide, allows synthesis array optically active indolenines with high yields and excellent enantioselectivities. A one-pot approach same has also been established further improve synthetic accessibility this protocol.

Язык: Английский

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Ligand-Controlled Regiodivergent Ring Expansion of Benzosilacyclobutenes with Alkynes en Route to Axially Chiral Silacyclohexenyl Arenes

Journal of the American Chemical Society, Год журнала: 2024, Номер unknown

Опубликована: Сен. 21, 2024

A ligand-controlled regiodivergent and enantioselective ring expansion of benzosilacyclobutenes with internal naphthyl alkynes has been achieved by adjusting the ligand cavity size. The (

Язык: Английский

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