[3+2] Cycloaddition of Rationally Designed Trisubstituted Cyclic α‐Chloroamide: an Alternative Strategy for Accessing Spirocyclic γ‐Lactam Architecture DOI
Yang Li,

Wei‐Fang Zuo,

Jianhua Chen

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 366(2), P. 269 - 276

Published: Nov. 30, 2023

Abstract Here we present a [3+2] cycloaddition of rationally designed trisubstituted cyclic α‐chloroamides, primarily those incorporating pharmacological pyrazolone cores, as potent synthons for synthesizing valuable spirocyclic γ‐lactam architectures. This protocol exhibits 52–96% yields, impressive substrate compatibility, and scale‐up capacity. Importantly, this study also represents one the rare examples that harness enaminone C−N bond cleavage to engineer relevant skeletons biological interest. Moreover, propose plausible mechanistic explanation elucidate outstanding chemical outcomes observed, thereby enriching synthetic toolbox chemistry α‐haloamide‐mediated reactions.

Language: Английский

Visible-Light-Driven Synergistic Se/Fe Catalysis for the Synthesis of 2-Aminoquinoline Derivatives DOI

Yan‐Ling Ji,

Hong Wang,

Xiang‐Hong He

et al.

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

Published: March 3, 2025

A visible-light-driven Se/Fe synergistic catalytic reaction between isocyanides and amines has been developed, employing air as the terminal oxidant. This efficient strategy offers facile access to 2-aminoquinoline scaffolds. The use of cost-effective readily available Fe(OTf)3 modulates selenium catalyst's oxidation state, enhancing method's environmental friendliness practicality. protocol is further distinguished by its good yields, broad substrate scope, mild conditions.

Language: Английский

Citations

1
Asymmetric Cascade Cyclization of Enynamides with Photogenerated Ketenes via Relay Gold and N-Oxide Catalysis DOI
Dan Liŭ,

Zhen‐Cao Shu,

Zhihan Zhang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 1741 - 1749

Published: Jan. 18, 2024

An asymmetric cascade cyclization of enynamides and α-diazoketones to produce chiral bicyclic lactams bearing all-carbon quaternary stereocenters is realized with up 95% yield, 98% ee, >19:1 dr. The combination visible light photoactivation the relay gold N-oxide catalysis in a process enabled facile generation controlled assembly two reactive intermediates, ketene aza-o-quinone methide. Theoretical calculations revealed stepwise [4 + 2] cycloaddition mechanism, stereochemistry by amide group catalyst. Remarkably, this study presents first example N-oxides serving as catalysts for illustrates how strategy could be promising means access significant heterocyclic scaffolds.

Language: Английский

Citations

5
Cooperative Gold(I)/DMAP Catalysis Enabled (2 + 3) Cycloadditions of Yne–Enones with Oxindole-Derived MBH Carbonates DOI

Hongli Zhao,

Laiping Yao,

Yiqiao Gu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(18), P. 3790 - 3795

Published: April 26, 2024

A cooperative gold(I)/DMAP system catalyzes the (2 + 3) cycloadditions of yne-enones with oxindole-derived Morita-Baylis-Hillman (MBH) carbonates, yielding diverse bispiro-cyclopentene oxindole products. The mild, scalable protocol demonstrates broad substrate scope and excellent chemo- diastereoselectivity. Mechanistic study reveals pivotal roles both catalysts in unique cycloaddition. This strategy showcases superiority achieving transformation chemoselectivity diastereoselectivity, unattainable through traditional monocatalytic methodologies.

Language: Английский

Citations

5
Catalyst-controlled regiodivergence and stereodivergence in formal cross-[4+2] cycloadditions: The unique effect of bismuth(III) DOI
Qiumeng Hou,

Chenxi Cai,

Shuai‐Jiang Liu

et al.

Science Advances, Journal Year: 2025, Volume and Issue: 11(13)

Published: March 26, 2025

The [4+2] cycloaddition is crucial for constructing six-membered rings in pharmaceuticals and natural products. Cross-[4+2] cycloadditions offer greater product diversity than traditional diene-dienophile reactions due to multiple possible pathways. However, precise control over regio- stereoselectivity various isomers remains a great challenge. This study reports catalyst-controlled regiodivergent formal cross-cycloadditions of acyclic dienes enones, significantly enhancing access diverse pyrazole-fused spirooxindoles. Chiral phosphoric acid (CPA) catalysis enables endoselective cycloadditions, while Bi(III) with CPA ligand yields [2+4] products high stereoselectivity. A Claisen rearrangement the adduct produces exo-selective product, further increasing stereochemical enabling synthesis six stereo-isomers from single substrate set. DFT calculations reveal that reverses regioselectivity by repositioning reactants pocket stabilizing enone oxygen’s negative charge. In addition, 3as demonstrates therapeutic potential against triple-negative breast cancer, an IC 50 8.5 μM MDA-MB-453 cells.

Language: Английский

Citations

0
Construction of Cyclopentanes Consisting of Five Stereocenters via NHC-Catalyzed Cascade Reactions of Enals with Oxindole-Dienones DOI

Yadi Niu,

Laiping Yao,

Hongli Zhao

et al.

Organic Letters, Journal Year: 2023, Volume and Issue: 25(47), P. 8445 - 8450

Published: Nov. 17, 2023

Despite the widespread presence of chiral cyclopentane motif, asymmetric synthesis cyclopentanes containing five stereocenters remains a formidable challenge. Here, we present an N-heterocyclic carbene (NHC)-catalyzed cascade reaction enal and oxindole-dienone, which allows access to spiroxindole featuring complete set centers on five-membered carbocycle. This strategy, characterized by formation multiple bonds centers, demonstrates broad substrate scope, exclusive diastereoselectivity, up 99:1 er.

Language: Английский

Citations

10
Chemoselective synthesis of bridged benzo[no]tetraphen-8-one via copper-catalyzed radical dimerization of 1-alkynylnaphthols DOI
Jianhua Chen, Jie Yang, Ke Xu

et al.

Tetrahedron Letters, Journal Year: 2024, Volume and Issue: 136, P. 154929 - 154929

Published: Jan. 26, 2024

Language: Английский

Citations

1
Bifunctional Lewis Base-Catalyzed (3 + 2) Cycloadditions of Pyrazolone-Derived MBH Carbonates with Arynes DOI

Laiping Yao,

Yiqiao Gu,

Yuling Wu

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(42), P. 9108 - 9113

Published: Oct. 16, 2024

The (3 + 2) cycloaddition of arynes with allylic ylides remains a formidable challenge because both intermediates are highly reactive and prone to spontaneous quenching. Here, we report pyrazolone MBH carbonates arynes, enabling the efficient synthesis diverse indene-fused spiropyrazolones. key is employing new bifunctional Lewis base catalyst facilitate

Language: Английский

Citations

0
[3+2] Cycloaddition of Rationally Designed Trisubstituted Cyclic α‐Chloroamide: an Alternative Strategy for Accessing Spirocyclic γ‐Lactam Architecture DOI
Yang Li,

Wei‐Fang Zuo,

Jianhua Chen

et al.

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 366(2), P. 269 - 276

Published: Nov. 30, 2023

Abstract Here we present a [3+2] cycloaddition of rationally designed trisubstituted cyclic α‐chloroamides, primarily those incorporating pharmacological pyrazolone cores, as potent synthons for synthesizing valuable spirocyclic γ‐lactam architectures. This protocol exhibits 52–96% yields, impressive substrate compatibility, and scale‐up capacity. Importantly, this study also represents one the rare examples that harness enaminone C−N bond cleavage to engineer relevant skeletons biological interest. Moreover, propose plausible mechanistic explanation elucidate outstanding chemical outcomes observed, thereby enriching synthetic toolbox chemistry α‐haloamide‐mediated reactions.

Language: Английский

Citations

1