Remote copper-catalyzed enantioselective substitution of yne-thiophene carbonates

Science China Chemistry, Год журнала: 2024, Номер 67(4), С. 1175 - 1180

Опубликована: Фев. 29, 2024

Язык: Английский

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

ACS Catalysis, Год журнала: 2024, Номер 14(12), С. 9244 - 9253

Опубликована: Июнь 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.

Язык: Английский

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Organocatalytic Asymmetric Synthesis of o-Carboranyl Amines

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

Опубликована: Янв. 14, 2025

Carboranyl amines are distinct from typical organic amines. Due to the electronic influence of carborane cage, they have low nucleophilicity and reluctant alkylate. Moreover, asymmetric synthesis chiral carboranes is still in its infancy. Herein we achieved first catalytic N-alkylation o-carboranyl amine, providing general access diverse secondary with high efficiency enantioselectivity under mild conditions. For time, organocatalysis was introduced chemistry. Key success use situ generated (naphtho-)quinone methides as alkylating reagents suitable acid catalysts. This protocol also applicable S-alkylation 1-SH-o-C2B10H11. Control experiments kinetic studies provided important insights into reaction mechanism, which likely involves rate-determining generation quinone methide followed by fast enantio-determining nucleophilic addition.

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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Photoredox/Copper-Catalyzed One-Pot Aminoalkylation/Cyclization of Alkenes with Primary Amines to Synthesize Polysubstituted γ-Lactams

Organic Letters, Год журнала: 2024, Номер 26(4), С. 845 - 849

Опубликована: Янв. 22, 2024

Visible-light-driven chemical transformation has emerged as a powerful tool for the synthesis of γ-lactams. However, during this transformation, α-bromoimides need to be pre-prepared. Herein, we report photoreodox/copper-catalyzed one-pot three-component reaction alkenes with primary amines construction In orthoquinones were generated via photocatalytic pathway, followed by attack Cu–amido complexes and intramolecular cyclization give This method represents simple synthetic route displaying broad functional group tolerance, including substrates bearing alcohols, ketones, heterocycles, esters, halides, alkynes, nitriles, ethers, etc.

Язык: Английский

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Organocatalytic Enantioselective 1,12‐Addition of Alkynyl Biphenyl Quinone Methides Formed In Situ

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(29)

Опубликована: Май 3, 2024

The chemistry of quinone methides formed in situ has been flourishing recent years. In sharp contrast, the development and utilization biphenyl are rare. this study, we achieved a remote stereocontrolled 1,12-conjugate addition for first time. presence suitable chiral phosphoric acid, alkynyl were generated from α-[4-(4-hydroxyphenyl)phenyl]propargyl alcohols, followed by enantioselective with indole-2-carboxylates. strategy enabled alcohols to serve as efficient allenylation reagents, providing practical access broad range axially allenes bearing (1,1'-biphenyl)-4-ol unit, which previously less accessible. Combined control experiments, density functional theory calculations shed light on reaction mechanism, indicating that enantioselectivity originates nucleophilic methides. Notably, not only versatile intermediates was confirmed but also organocatalytic 1,12-addition established.

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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Organocatalytic Remote Stereocontrolled Synthesis of Tetrasubstituted Allenes via Asymmetric 1,8‐Addition of Propargylic Aza‐p‐Quinone Methides

Advanced Synthesis & Catalysis, Год журнала: 2024, Номер 366(5), С. 1078 - 1083

Опубликована: Янв. 17, 2024

Abstract An organocatalytic remote stereocontrolled 1,8‐conjugated addition of in situ formed propargylic aza‐ p ‐QMs from α‐(4‐aminophenyl) alcohols and indole‐2‐carboxylates was developed, affording axially chiral tetrasubstituted allenes 62–99% yield with 52–99% ee. The synthetic strategy not only enriches the chemistry ‐quinone methides, but also provides an alternative tool for preparation allenes.

Язык: Английский

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Catalytic Asymmetric Cyclizative Rearrangement of Anilines and Vicinal Diketones to Access 2,2‐Disubstituted Indolin‐3‐ones

Advanced Science, Год журнала: 2024, Номер 11(25)

Опубликована: Апрель 24, 2024

Abstract The efficient synthesis of chiral 2,2‐disubstituted indolin‐3‐ones is great importance due to its significant synthetic and biological applications. However, catalytic enantioselective methods for de novo such heterocycles remain scarce. Herein, a novel cyclizative rearrangement readily available anilines vicinal diketones the one‐step construction enantioenriched presented. reaction proceeds through self‐sorted [3+2] heteroannulation/regioselective dehydration/1,2‐ester shift process. Only phosphoric acid employed promote entire sequence simplify manipulation this protocol. Various common aniline derivatives are successfully applied asymmetric as 1,3‐binuclephiles first time. Remarkably, observed stereoselectivity proposed originate from an amine‐directed regio‐ ortho ‐Csp 2 ‐H addition ketones. A range transformations resulting products demonstrated well.

Язык: Английский

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An Axially Chiral Styrene–Phosphine Ligand for Pd-Catalyzed Asymmetric N-Alkylation of Indoles

The Journal of Organic Chemistry, Год журнала: 2023, Номер 88(20), С. 14719 - 14727

Опубликована: Окт. 4, 2023

An efficient palladium-catalyzed enantioselective direct N-alkylation of indoles using a novel type axially chiral styrene-phosphine ligand SJTU-PHOS-1 was developed. This reaction demonstrated good functional group compatibility and wide range scope substrates in mild conditions. Moreover, the DFT calculations expounded coordination mode metal catalyst enantioselectivity control.

Язык: Английский

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