Transition-metal-catalyzed atroposelective synthesis of axially chiral styrenes

Chemical Communications, Journal Year: 2023, Volume and Issue: 59(85), P. 12669 - 12684

Published: Jan. 1, 2023

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

Language: Английский

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Photocatalytic Z/E isomerization unlocking the stereodivergent construction of axially chiral alkene frameworks

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: April 16, 2024

Abstract The past century has witnessed a large number of reports on the Z / E isomerization alkenes. However, vast majority them are still limited to di- and tri-substituted stereospecific tetrasubstituted alkenes remains be an underdeveloped area, thus lacking in stereodivergent synthesis axially chiral Herein we report atroposelective alkene analogues by asymmetric allylic substitution-isomerization, followed their via triplet energy transfer photocatalysis. In this regard, N -vinylquinolinones is achieved efficiently. Mechanistic studies indicate that benzylic radical generation distribution two key factors for preserving enantioselectivities compounds.

Language: Английский

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

Precision Chemistry, Journal Year: 2024, Volume and Issue: 2(5), P. 208 - 220

Published: April 23, 2024

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

Language: Английский

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

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(30)

Published: May 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.

Language: Английский

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Construction of Non-Biaryl Atropisomeric Amide Scaffolds Bearing a C–N Axis via Enantioselective Catalysis

Molecules, Journal Year: 2022, Volume and Issue: 27(19), P. 6583 - 6583

Published: Oct. 4, 2022

The significant scaffold offered by atropisomeric amides with a C–N chiral axis has been extensively utilized for pharmaceuticals, agricultural science, and organic syntheses. As result, the field of atropisomer synthesis attracted considerable interest within chemistry communities. To date, range catalytic atroposelective approaches reported efficient construction these challenging scaffolds. However, greatly concise highly useful methodologies compounds, focusing on transition-metal, amine, phosphoric acid catalysis reactions, etc., are still desirable. Hence, it is indispensable to succinctly systematically present all such reports means disclosing mechanistic analysis application, as well challenges issues associated establishment atropisomers. In this review, we summarize development asymmetric synthetic strategies access non-biaryl atropisomers rotating around axis, including reaction methods, mechanism, late-stage transformations, applications.

Language: Английский

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Asymmetric Allylic Substitution‐Isomerization for the Modular Synthesis of Axially Chiral N‐Vinylquinazolinones

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: Aug. 16, 2023

Abstract Axially chiral N ‐substituted quinazolinones are important bioactive molecules, which presented in many synthetic drugs. However, most strategies toward their atroposelective synthesis mainly limited to the axially arylquinazolinone frameworks. The development of modular methods access diverse quinazolinone‐based atropisomers remains scarce and challenging. Herein, we report regio‐ ‐vinylquinazolinones via strategy asymmetric allylic substitution‐isomerization. catalysis system utilized both transition‐metal organocatalysis efficiently afford trisubstituted tetrasubstituted ‐vinylquinazolinone atropisomers, respectively. With meticulous design β‐substituted substrates, Z ‐ E ‐tetrasubstituted were obtained good yields high enantioselectivities.

Language: Английский

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Atroposelective Synthesis of C−N Vinylindole Atropisomers by Palladium‐Catalyzed Asymmetric Hydroarylation of 1‐Alkynylindoles

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(45)

Published: Sept. 25, 2023

Transition-metal-catalyzed hydroarylation of unsymmetrical internal alkynes remains challenging because the difficulty in controlling regioselectivity and stereoselectivity. Moreover, enantioselective using organoboron reagents has not been reported. Herein, we report for first time that palladium compounds can catalyze 1-alkynylindoles with organoborons synthesis chiral C-N atropisomers. A series rarely reported vinylindole atropisomers was synthesized excellent regio-, stereo- (Z-selectivity), enantioselectivity under mild reaction conditions. The ready availability simplicity, high stereoselectivity, good functional group tolerance this catalytic system make it highly attractive.

Language: Английский

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Iridium-Catalyzed Asymmetric Allylic Substitution with Sequential Boron Incorporation

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: May 9, 2025

An iridium-catalyzed asymmetric allylic substitution with sequential boron incorporation is reported. The reaction accommodates a wide range of substrates, affording chiral N,O-bidentate difluoroboron complexes in excellent yields high enantioselectivities. Furthermore, decigram-scale reaction, synthetic transformations, as well photophysical property investigations the are explored.

Language: Английский

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Atroposelective Construction of Tetrasubstituted Axially Chiral Alkene Frameworks

Synthesis, Journal Year: 2023, Volume and Issue: 56(12), P. 1862 - 1872

Published: Dec. 14, 2023

Abstract The construction of axially chiral alkene frameworks is currently one hottest topics in the field organic synthetic chemistry. Compared to traditional molecules, such as biaryls, heterobiaryls, and anilides, synthesis alkenes far more challenging, especially for acyclic tetrasubstituted analogues. In this review, we summarized development strategies analogues, including asymmetric difunctionalization, C–H functionalization, cross-coupling, (dynamic) kinetic resolution, allylic substitution-isomerization. 1 Introduction 2 Synthesis Cyclic Tetrasubstituted Axially Chiral Alkenes 3 Acyclic 4 Summary Outlook

Language: Английский

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Progress in Asymmetric Catalytic Synthesis of C—N Axis Chiral Compounds

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(2), P. 349 - 349

Published: Jan. 1, 2024

Enantioenriched C-N axial chiral compounds are ubiquitous in many important field, such as natural products, drugs and ligands.Therefore, efficient construction of axis chirality through asymmetric catalytic synthesis has attracted more attention research interest.In this review, the recent progress been discussed, mainly from three aspects: desymmetrization prochiral molecules or kinetic resolution racemates, atroposelective functionalization axis, coupling reaction.The topic focuses on evolution system key factors control.The existing problems future development direction field also discussed.This paper is a timely systematic review will stimulate extensive interest.

Language: Английский

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