Synergistic Photoredox and Palladium-Catalyzed 1,3-Acyloxyallylation of Aryl Cyclopropanes with Allyl Esters DOI

Lixu Ren,

Jun Wei, Yingfeng Yu

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 17503 - 17509

Published: Nov. 13, 2024

A synergistic photoredox and palladium-catalyzed 1,3-acyloxyallylation of aryl cyclopropanes with allyl esters has been developed. Aryl are unprecedentedly employed as radical precursors in allylation reactions acting bifunctional reagents, thereby providing acyloxy groups nucleophiles the moiety a scavenger for formation benzylic C(sp3)–C(sp3) bonds. This redox-neutral reaction exhibits 100% atom economy good functional group tolerance successfully applied to late-stage modification pharmaceutical derivatives.

Language: Английский

Eu(OTf)3‐Catalyzed Formal Dipolar [4π+2σ] Cycloaddition of Bicyclo‐[1.1.0]butanes with Nitrones: Access to Polysubstituted 2‐Oxa‐3‐azabicyclo[3.1.1]heptanes DOI
Jian Zhang,

Jia‐Yi Su,

Hanliang Zheng

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(13)

Published: Jan. 30, 2024

Abstract Herein, we have synthesized multifunctionalized 2‐oxa‐3‐azabicyclo[3.1.1]heptanes, which are considered potential bioisosteres for meta ‐substituted arenes, through Eu(OTf) 3 ‐catalyzed formal dipolar [4π+2σ] cycloaddition of bicyclo[1.1.0]butanes with nitrones. This methodology represents the initial instance fabricating bicyclo[3.1.1]heptanes adorned multiple heteroatoms. The protocol exhibits both mild reaction conditions and a good tolerance various functional groups. Computational density theory calculations support that mechanism likely involves nucleophilic addition nitrones to bicyclo[1.1.0]butanes, succeeded by an intramolecular cyclization. synthetic utility this novel has been demonstrated in concise synthesis analogue Rupatadine.

Language: Английский

Citations

49
Cooperative Photoredox and Cobalt‐Catalyzed Acceptorless Dehydrogenative Functionalization of Cyclopropylamides towards Allylic N,O‐Acyl‐acetal Derivatives DOI

Haohao Huang,

Xinjun Luan, Zhijun Zuo

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(24)

Published: April 13, 2024

Abstract We disclose herein a novel photoredox and cobalt co‐catalyzed ring‐opening/acceptorless dehydrogenative functionalization of mono‐donor cyclopropanes. This sustainable atom‐economic approach allows the rapid assembly wide range allylic N,O ‐acyl‐acetal derivatives. The starting materials are readily available reaction features mild conditions, broad substrate scope, excellent functional group compatibility. optimized conditions accommodate assorted cycloalkylamides primary, secondary, tertiary alcohols, with applications in late‐stage pharmaceutically relevant compounds, stimulating further utility medicinal chemistry. Moreover, selective nucleophilic substitutions various carbon nucleophiles were achieved one‐pot fashion, offering reliable avenue to access some cyclic acyclic

Language: Английский

Citations

8
Photocatalytic Regioselective Redox-Neutral 1,3-Oxypyridylation of Aryl Cyclopropanes DOI
Dongjie Li,

X.-Y. Liu,

You-Zhi Liao

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(38), P. 8063 - 8068

Published: Sept. 16, 2024

Pyridines and cyclopropanes are important structural units in chemistry. Herein, we introduce a photoredox-catalyzed approach for the ring opening 1,3-oxypyridylation of aryl using 4-cyanopyridines carboxylic acids. This sequential process involves single-electron oxidation cyclopropane, leading to nucleophilic radical pyridylation at benzylic position. The redox-neutral reaction exhibits high regioselectivity under mild conditions, offering broad substrate scope wide applicability.

Language: Английский

Citations

4
Visible light-mediated organocatalyzed 1,3-aminoacylation of cyclopropane employing N-benzoyl saccharin as bifunctional reagent DOI Creative Commons
Mingrui Li,

Yingtao Wu,

Song Xiao

et al.

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

Published: Oct. 16, 2024

The carboamination of unsaturated molecules using bifunctional reagents is considered an attractive approach for the synthesis nitrogen-containing compounds. However, C-N have never been employed in cyclopropane. In this study, we use N-heterocyclic carbene (NHC), N-benzoyl saccharin, as a reagent and photoredox catalyst dual-catalyzed 1,3-aminoacylation NHCs play multiple roles, functioning Lewis base catalysts to activate bonds, promoting oxidative quenching process PC*, acting efficient acyl radical transfer formation C-C bonds. between excited-state PC* NHC adduct key photooxidation generality aryl cyclopropanes.

Language: Английский

Citations

4
Eu(OTf)3‐Catalyzed Formal Dipolar [4π+2σ] Cycloaddition of Bicyclo‐[1.1.0]butanes with Nitrones: Access to Polysubstituted 2‐Oxa‐3‐azabicyclo[3.1.1]heptanes DOI
Jian Zhang,

Jia‐Yi Su,

Hanliang Zheng

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(13)

Published: Jan. 30, 2024

Abstract Herein, we have synthesized multifunctionalized 2‐oxa‐3‐azabicyclo[3.1.1]heptanes, which are considered potential bioisosteres for meta ‐substituted arenes, through Eu(OTf) 3 ‐catalyzed formal dipolar [4π+2σ] cycloaddition of bicyclo[1.1.0]butanes with nitrones. This methodology represents the initial instance fabricating bicyclo[3.1.1]heptanes adorned multiple heteroatoms. The protocol exhibits both mild reaction conditions and a good tolerance various functional groups. Computational density theory calculations support that mechanism likely involves nucleophilic addition nitrones to bicyclo[1.1.0]butanes, succeeded by an intramolecular cyclization. synthetic utility this novel has been demonstrated in concise synthesis analogue Rupatadine.

Language: Английский

Citations

3
Electrochemical [3+3] Annulation of Phenol and Hydrazone: Synthesis of 1,3,4-Oxadiazines DOI
Jiahui Zhang, Yang‐Yang Hu,

Yuge Ran

et al.

The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 19, 2025

A novel [3+3] cyclization reaction between phenol and hydrazone was successfully developed under electrochemically driven conditions. This provided access to a diverse array of 1,3,4-oxadiazinane compounds in consistently high yields, reaching up 87%. Notably, the exhibited remarkable tolerance toward broad spectrum both substrates, underscoring its versatility. Moreover, protocol distinguished itself by exceptional atom step economy, facilitating efficient construction functionalized 1,3,4-oxadiazines. The synthetic utility this approach further exemplified scalability, as demonstrated gram-scale reactions, substrate scope.

Language: Английский

Citations

0
Recent Advancements in Metal‐Free Catalysis for Cyclopropane Ring Cleavage DOI Open Access
Amit Pramanik, Asit Kumar Das, Sanjay Bhar

et al.

ChemistrySelect, Journal Year: 2025, Volume and Issue: 10(9)

Published: March 1, 2025

Abstract Over the last decade, there have been notable advances in field of ring opening reaction numerous cyclopropane derivatives under metal‐free conditions including donor–acceptor cyclopropanes, acceptor‐activated alkylidenecyclopropanes, cyclopropyl alcohols, and vinylidenecyclopropanes. This review article aims to offer a comprehensive overview on cleavage reactions cyclopropanes using Bronsted Lewis acids, organic inorganic bases, TCT‐DMF, ionic liquids etc. Photoinduced catalyst‐free are also accentuated this review.

Language: Английский

Citations

0
Visible light-mediated 1,3-acylative chlorination of cyclopropanes employing benzoyl chloride as bifunctional reagents in NHC catalysis DOI
Mingrui Li, Song Xiao,

Xueyun Lu

et al.

Science China Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: March 10, 2025

Language: Английский

Citations

0
Converting Strain Release into Aromaticity Loss for Activation of Donor–Acceptor Cyclopropanes: Generation of Quinone Methide Traps for C-Nucleophiles DOI
Vitaly V. Shorokhov, Beauty K. Chabuka,

Timur P. Tikhonov

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 12, 2024

Here, we present a new approach for the activation of donor-acceptor cyclopropanes in ring-opening reactions, which does not require use Lewis or Brønsted acid as catalyst. Donor-acceptor containing phenolic group donor undergo deprotonation and isomerization to form corresponding quinone methides. This innovative strategy was applied achieve (4 + 1)-annulation with sulfur ylides, affording functionalized dihydrobenzofurans. Additionally, generated

Language: Английский

Citations

3
An Intermolecular Hydroarylation of Unactivated Arylcyclopropane via Re2O7/HFIP-Mediated Ring Opening DOI

Liqun Hu,

Yao Xiang,

Xiao‐Bing Lan

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(10), P. 2085 - 2090

Published: March 5, 2024

In this paper, we describe a Re2O7-mediated ring-opening arylation of unactivated arylcyclopropane because its functionalization with various arenes via Friedel–Crafts-type reactivity. This protocol allows facile access to functionalized 1,1-diaryl alkanes and is characterized by broad substrate scope, mild reaction conditions, high efficiency, atom economy. Both density functional theory calculations deuterium labeling experiments were carried out justify the indispensable role HFIP in transformation pointed ring opening being rate-determining step.

Language: Английский

Citations

2