Remote copper-catalyzed enantioselective substitution of yne-thiophene carbonates

Science China Chemistry, Journal Year: 2024, Volume and Issue: 67(4), P. 1175 - 1180

Published: Feb. 29, 2024

Language: Английский

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Copper-Catalyzed Asymmetric Yne-Allylic Substitution Using Electron-Rich Arenes

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(4), P. 2746 - 2757

Published: Feb. 7, 2024

Remote stereocontrol in transition-metal catalysis is a challenging but interesting research topic. In this work, we achieved copper-catalyzed asymmetric yne-allylic substitution using electron-rich arenes and acyclic carbonates through remote enantioselectivity control. The reaction delivers variety of enantioenriched products that contain diverse set valuable moieties, such as conjugated enynes, indoles, indolizines, allenes, dihydrofurans, which are widely used organic synthesis act key units bioactive molecules natural products. synthetic value protocol has been demonstrated series further transformations, mechanistic studies have conducted to gain more insight into the reaction.

Language: Английский

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Remote Enantioselective [4 + 1] Annulation with Copper-Vinylvinylidene Intermediates

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(46), P. 21347 - 21355

Published: Nov. 11, 2022

The first copper-catalyzed enantioselective [4 + 1] annulation of yne-allylic esters with 1,3-dicarbonyl compounds was realized through an elegant remote stereocontrol strategy. very ε regioselective nucleophilic substitution developed by employing a novel chiral copper-vinylvinylidene species from the new C4 synthon esters. Thus, greatly diverse spirocycles were obtained ample scope and excellent levels chemo-, regio-, enantioselectivities. Moreover, detailed mechanistic studies suggest Conia-ene cascade pathway on stereochemical induction progress.

Language: Английский

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Copper-catalysed convergent regio- and enantioselective alkynylallylic substitution

Nature Synthesis, Journal Year: 2022, Volume and Issue: 2(1), P. 37 - 48

Published: Oct. 24, 2022

Language: Английский

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Copper‐Catalyzed Remote Enantioselective Sulfonylation of Yne‐Allylic Esters with Sodium Sulfinates

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(52)

Published: Nov. 13, 2023

Impressive progress has been made in the copper-catalyzed asymmetric propargylic substitution (APS) reaction, but its use remote yne-allylic remains a challenging topic. Herein, we report first enantioselective sulfonylation of esters with sodium sulfinates. The reaction is assumed to occur via copper-vinylvinylidene species as key reactive intermediate. readily available starting materials, mild conditions, and excellent regio-, enantio- stereoselectivity, well broad substrate scope (>70 examples), show practicality attractiveness this method.

Language: Английский

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Asymmetric Substitution by Alkynyl Copper Driven Dearomatization and Rearomatization

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(47)

Published: Oct. 16, 2023

Abstract Catalytic asymmetric transformations by dearomatization have developed into a widely applicable synthetic strategy, but heavily relied on the use of arenes bearing heteroatom. In this case, is facilitated involvement p ‐orbital electron Different from conventional substrate‐dependent model, here we demonstrate that activation d transition‐metal center can serve as driving force for dearomatization, and applied to development novel alkynyl copper remote substitution reaction. A newly modified PyBox chiral ligand enables construction valuable diarylmethyl triarylmethyl skeletons in high enantioselectivities. An unexpected tandem process involving sequential substitution/cyclization/1,5‐H shift leads formation enantioenriched C−N axis. gram‐scale reaction various downstream highlight robustness method potential products. Preliminary mechanistic studies reveal mononuclear Cu‐catalyzed process.

Language: Английский

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Asymmetric copper-catalyzed alkynylallylic monofluoroalkylations with fluorinated malonates

Chemical Communications, Journal Year: 2024, Volume and Issue: 60(31), P. 4210 - 4213

Published: Jan. 1, 2024

The unprecedented copper-catalyzed asymmetric alkynylallylic monofluoroalkylation reaction is described

Language: Английский

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Asymmetric Dearomatization of Nonfunctionalized 1-Naphthols via Copper-Catalyzed Enantioselective [4 + 1] Spiroannulation

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(12), P. 9244 - 9253

Published: June 3, 2024

Catalytic asymmetric dearomatization (CADA) is a powerful tool for the rapid construction of complex chiral three-dimensional cyclic molecules featuring quaternary carbon centers from readily available arenes. However, ubiquitous nonfunctionalized 1-naphthols to afford remains challenging and undeveloped. This study reports dearomative [4 + 1] spiroannulation via copper catalysis. reaction features highly chemo-, regio-, stereoselective nucleophilic addition intramolecular annulation cascade reactive π-extended copper-allenylidene, thus enabling practical synthesis range valuable spirocyclic enones bearing stereocenter with high efficiency. Furthermore, this protocol applicable phenols. Control experiments supported substitution-annulation mechanism by excluding process involving 1,3-sigmatropic shift. Preliminary biological activity studies indicated that synthesized hold significant promise as anticancer agents inducing tumor cell apoptosis.

Language: Английский

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Recent advances in copper-catalyzed asymmetric propargylic substitution

Tetrahedron Chem, Journal Year: 2024, Volume and Issue: 11, P. 100082 - 100082

Published: July 3, 2024

Language: Английский

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Enantioselective Copper-Catalyzed Dearomative Spiroannulation of β-Naphthols or Indoles with Yne-Allylic Esters

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(12), P. 9254 - 9264

Published: June 3, 2024

Catalytic asymmetric dearomatization reactions of α-unsubstituted β-naphthols are very challenging due to the high energy barrier resulting from loss aromaticity. Herein, we describe an example enantioselective catalytic dearomative spiroannulation with yne-allylic esters. The success this reaction relied on copper-catalyzed remote strategy using esters as bis-electrophilic reagents. This transformation features mild conditions, broad functional group tolerance, and extensive substrate scope, thereby facilitating efficient construction array enantioenriched naphthalene-2-one spiroindolenine derivatives. Experimental studies density theory calculations establish pathway origin stereoselectivity.

Language: Английский

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