X-ray Absorption and Electron Paramagnetic Resonance Guided Discovery of the Cu-Catalyzed Synthesis of Multiaryl-Substituted Furans from Aryl Styrene and Ketones Using DMSO as the Oxidant

Wu, Yong; Huang, Zhiyuan; Luo, Yi; Liu, Dong; Deng, Yi; Hong, Yi; Lee, Jyh‐Fu; Pao, Chih‐Wen; Chen, Jeng-Lung; Lei, Aiwen

doi:10.1021/acs.orglett.7b00865

Cited by 49 publications

(17 citation statements)

References 46 publications

(10 reference statements)

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“…under the deactivating, oxidative nature of the DMSO solvent. The above experiments with a model fluorogenic "click" reaction and different reaction media provide solid support that the intra-chain distribution of catalytic sites has an important effect on the catalytic activity of "clickase" SCNPs, especially in solvents with significant oxidative nature like DMSO [67].…”

Section: Discussionmentioning

confidence: 69%

“…Remarkably, the difference in catalytic activity observed (Ck-SCNPs2 > Ck-SCNPs1 > CuSO4) was more notorious in DMSO than in aqueous THF. The slower reaction rate in DMSO can be attributed -to a large extent-to the oxidant power of this solvent [67] that oxidizes a certain amount of Cu(I) ions generated by NaAsc to Cu(II) ions, the latter being inactive for the "click" reaction. Interestingly enough, the presence of cluster of Cu ions in the case of Ck-SCNPs2 was found beneficial for improving the stability and effectiveness of the "clickase" SCNPs…”

Section: Resultsmentioning

confidence: 99%

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“Clickase” Single-Chain Nanoparticles: Effect of Intra-Chain Distribution of Catalytic Sites on Catalytic Activity

Asenjo-Sanz¹,

Claros²,

González³

et al. 2021

Preprint

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“Clickase” single-chain nanoparticles (Ck-SCNPs) are folded, enzyme-mimetic unimolecular polymeric nano-objects containing copper (Cu) ions able to catalyze the azide-alkyne Huisgen cycloaddition reaction in water and/or selected organic solvents, often in the presence of a reductant. Herein, we investigate the effect of morphology on catalytic activity of Ck-SCNPs synthesized by means of two different routes. An amphiphilic random copolymer composed of oligo(ethylene glycol) methyl ether methyl methacrylate (OEGMA) and 2-acetoacetoxy ethyl methacrylate (AEMA) units was used as precursor of these Ck-SCNPs. Folding was promoted through metal complexation between Cu(II) ions and beta-ketoester-containing AEMA moieties. The first route resulted in Ck-SCNPs1 containing Cu ions homogeneously distributed within each nanoparticle, whereas the second one promoted intra-chain clustering of Cu ions inside Ck-SCNPs2. A model fluorogenic “click” reaction between 9-(azidomethyl)anthracene and phenylacetylene, which was catalyzed either by Ck-SCNPs1 or Ck-SCNPs2, was used to unravel the effect of morphology on catalytic activity. This work paves the way to improve the catalytic activity of metallo-folded SCNPs through control of the intra-chain distribution of catalytic sites.

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Section: Discussionmentioning

confidence: 69%

Section: Resultsmentioning

confidence: 99%

“Clickase” Single-Chain Nanoparticles: Effect of Intra-Chain Distribution of Catalytic Sites on Catalytic Activity

Asenjo-Sanz¹,

Claros²,

González³

et al. 2021

Preprint

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“…[147] 2,3-Diphenyl-4H-indeno[1,2-b]furan 199 was prepared by the oxidative coupling of deoxybenzoin and indene promoted by CuCl 2 ; the proposed reaction mechanism included the formation of an α-keto radical followed by the addition of this radical to indene (Scheme 30). [148]…”

Section: H-indeno[12-b]furanmentioning

confidence: 99%

“…Preparation of 2,3-diphenyl-4H-indeno[1,2-b]furan and proposed reaction mechanism. [148] Scheme 31. Synthesis of 4H-indeno[1,2-b]thiophene 201.…”

Section: H-indeno[12-b]thiophenementioning

confidence: 99%

Synthesis of Heteroarene‐Fused Cyclopentadienes and Related Compounds Suitable for Metallocene Preparation

Nifant’ev

Ivchenko

2020

Adv Synth Catal

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Metallocene catalysis is widely used in transformations of unsaturated organic compounds, including the bulk industrial synthesis of polyolefins. Over the last few decades, the electronic and structural properties of their η5‐coordinated ligands have been modified by introducing electron‐donating, electron‐withdrawing, and sterically hindered substituents to obtain desirable catalytic properties for the metallocenes. An efficient way to design η5‐coordinated ligands is to exploit the annelation of heterocyclic fragments with a cyclopentadiene ring. In the present review, we summarize, systematize, and analyze synthetic approaches to heterocycle‐fused cyclopentadienes suitable for metallocene catalyst preparation.

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“…Similarly in 2017, Lei and co-workers reported a facile CuCl 2 -catalyzed oxidative cyclization of aryl ketones and styrenes towards the synthesis of multisubstituted furan derivatives. 43 Interestingly, through X-ray absorption and electron paramagnetic studies they revealed that DMSO, besides serving as a solvent, plays the crucial role of an oxidant to promote the oxidation of Cu(I) to Cu(II).…”

Section: Short Review Syn Thesismentioning

confidence: 99%

Metal-Catalyzed Oxidative Coupling of Ketones and Ketone Enolates

Murarka

Antonchick

2018

Synthesis

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Recent years have witnessed a significant advancement in the field of radical oxidative coupling of ketones towards the synthesis of highly useful synthetic building blocks, such as 1,4-dicarbonyl compounds, and biologically important heterocyclic and carbocyclic compounds. Besides oxidative homo- and cross-coupling of enolates, other powerful methods involving direct C(sp3)–H functionalizations of ketones have emerged towards the synthesis of 1,4-dicarbonyl compounds. Moreover, direct α-C–H functionalization of ketones has also allowed an efficient access to carbocycles and heterocycles. This review summarizes all these developments made since 2008 in the field of metal-catalyzed/promoted radical-mediated functionalization of ketones at the α-position.1 Introduction2 Synthesis of 1,4-Dicarbonyl Compounds3 Synthesis of Heterocyclic Scaffolds4 Synthesis of Carbocyclic Scaffolds5 Conclusion

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X-ray Absorption and Electron Paramagnetic Resonance Guided Discovery of the Cu-Catalyzed Synthesis of Multiaryl-Substituted Furans from Aryl Styrene and Ketones Using DMSO as the Oxidant

Cited by 49 publications

References 46 publications

“Clickase” Single-Chain Nanoparticles: Effect of Intra-Chain Distribution of Catalytic Sites on Catalytic Activity

“Clickase” Single-Chain Nanoparticles: Effect of Intra-Chain Distribution of Catalytic Sites on Catalytic Activity

Synthesis of Heteroarene‐Fused Cyclopentadienes and Related Compounds Suitable for Metallocene Preparation

Metal-Catalyzed Oxidative Coupling of Ketones and Ketone Enolates

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