Probing the support effect at the molecular level in the polyaniline-supported palladium nanoparticle-catalyzed Ullmann reaction of aryl iodides

Liu, Yonghong; Tang, Daliang; Cao, Kuanhong; Yu, Lei; Han, Jie; Xu, Qing

doi:10.1016/j.jcat.2018.01.026

Cited by 57 publications

(32 citation statements)

References 44 publications

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“…Furthermore, the homo- and cross-coupling of a series of alkaloids, amino acids and steroids exemplifies the robustness of this protocol in the functionalization of biologically active molecules. During the preparation of our manuscript, Xu and co-workers reported a Pd@PANIs-catalyzed Ullmann reaction of simple aryl iodides with stoichiometric N 2 H 4 as a reductant 46 . We anticipate that this traceless mediator conception will inspire strategies and opportunities to utilize hydrazine in sustainable chemical synthesis.…”

Section: Discussionmentioning

confidence: 99%

N2H4 as traceless mediator for homo- and cross- aryl coupling

Qiu

et al. 2018

Nat Commun

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Transition-metal catalyzed couplings of aryl halides or arenes with aryl organometallics, as well as direct reductive coupling of two aryl halides, are the predominant methods to synthesize biaryls. However, stoichiometric amounts of metals are inevitably utilized in these reactions, either in the pre-generation of organometallic reagents or acting as reductant in situ, thus producing quantitative metal waste. Herein, we demonstrate that this longstanding challenge can be overcome with N2H4 as a metal surrogate. The fundamental innovation of this strategy is that N2 and H2 are generated as side products, which readily escape from the system after the reaction. The success of both homo- and cross-coupling of various aryl electrophiles bearing a wide range of functional groups manifests the powerfulness and versatility of this strategy. Furthermore, both homo- and cross-couplings of a series of alkaloids, amino acids and steroids exemplify application of this protocol in the functionalization of biologically active molecules.

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Section: Discussionmentioning

confidence: 99%

N2H4 as traceless mediator for homo- and cross- aryl coupling

Qiu

et al. 2018

Nat Commun

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“…Liu et al prepared a series of polyaniline-supported palladium nanocatalysts for the Ullmann homocoupling reaction of aryl iodides to form biaryls. It was observed that the cata-lyst activity can be tuned by introducing electron-donating groups (Scheme 8) [74].…”

Section: Journal Of Nanomaterialsmentioning

confidence: 99%

Recent Developments in Nanostructured Palladium and Other Metal Catalysts for Organic Transformation

Hussain

Kamal

Hossain

2019

Journal of Nanomaterials

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Nanocatalysis is an emerging field of research and is applicable to nearly all kinds of catalytic organic conversions. Nanotechnology is playing an important role in both industrial applications and academic research. The catalytic activities become pronounced as the size of the catalyst reduces and the surface area-to-volume ratio increases which ultimately enhance the activity and selectivity of nanocatalysts. Similarly, the morphology of the particles also has a great impact on the activity and selectivity of nanocatalysts. Moreover, the electronic properties and geometric structure of nanocatalysts can be affected by polar and nonpolar solvents. Various forms of nanocatalysts have been reported including supported nanocatalysts, Schiff-based nanocatalysts, graphene-based nanocatalysts, thin-film nanocatalysts, mixed metal oxide nanocatalysts, magnetic nanocatalysts, and core-shell nanocatalysts. Among a variety of different rare earth and transition metals, palladium-based nanocatalysts have been extensively studied both in academia and in the industry because of their applications such as in carbon-carbon cross-coupling reactions, carbon-carbon homocoupling reactions, carbon-heteroatom cross-coupling reactions, and C-H activation, hydrogenation, esterification, oxidation, and reduction. The current review highlights the recent developments in the synthesis of palladium and some other metal nanocatalysts and their potential applications in various organic reactions.

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“…The anchoring of Mo-containing active species onto a suitable organic "support" might retain their high selectivity while endowing an extra catalytic performance derived from the organic "support". Notably, polyaniline (PAN) has recently received particular interest in catalytic applications as a heterogeneous organic support owing to its facile synthesis, air-stable performance, good dispersion of active species, and the pseudo-homogeneous character in organic solvents [20,[37][38][39][40][41][42][43][44]. In our group, we found that the functionalized PANs exhibited promising catalytic performance towards the dehydration of fructose into furans [45][46][47].…”

Section: Introductionmentioning

confidence: 94%

One-Pot Synthesis of 2,5-Diformylfuran from Fructose by Bifunctional Polyaniline-Supported Heteropolyacid Hybrid Catalysts

Liu

Dai

et al. 2019

Catalysts

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We report the preparation of bifunctional hybrid catalysts by supporting H3PMo12O40 (PMo12) heteropolyacid (HPA) on polyaniline (PAN) or formyl-functionalized PAN (F-PAN) for the “one-pot” and “one-step” synthesis of 2,5-diformylfuran (DFF) from fructose via 5-hydroxymethylfurfural (HMF) intermediate. We show that the PMo12 HPA is the main active species for both fructose dehydration and HMF oxidation owing to its Brønsted acidic and redox characters. However, the anchoring of PMo12 on PAN reduces the Brønsted acidity by acid–base interaction between protons in HPA and quinoid diimine structure in PAN, thereby reducing the dehydration performance. We demonstrate that the catalytic dehydration performance of the hybrid catalyst could be strengthened by grafting formyl groups on PAN before HPA anchoring. The highest DFF yield of 76.7% is obtained by conducting the “one-pot” reaction over the 40-PMo12/F3-PAN catalyst at 413 K for 7 h in air, wherein the side-reactions of fructose or HMF degradation and HMF rehydration have been significantly reduced. This hybrid catalyst is reusable without significant activity loss, highlighting the designing of stable inorganic–organic hybrid catalysts for producing valuable hexose-derived platform chemicals.

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Probing the support effect at the molecular level in the polyaniline-supported palladium nanoparticle-catalyzed Ullmann reaction of aryl iodides

Cited by 57 publications

References 44 publications

N2H4 as traceless mediator for homo- and cross- aryl coupling

N2H4 as traceless mediator for homo- and cross- aryl coupling

Recent Developments in Nanostructured Palladium and Other Metal Catalysts for Organic Transformation

One-Pot Synthesis of 2,5-Diformylfuran from Fructose by Bifunctional Polyaniline-Supported Heteropolyacid Hybrid Catalysts

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