Si-Gly-CD-PdNPs as a hybrid heterogeneous catalyst for environmentally friendly continuous flow Sonogashira cross-coupling

Ferlin, Francesco; Sciosci, Daniele; Valentini, Federica; Menzio, Janet; Cravotto, Giancarlo; Martina, Katia; Vaccaro, Luigi

doi:10.1039/d1gc02490f

Cited by 16 publications

(9 citation statements)

References 82 publications

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“…Later, the same group further developed another heterogeneous hybrid palladium catalyst supported onto a silica/β‐cyclodextrin matrix ( Si‐Gly‐CD‐PdNPs ) in continuous flow Sonogashira coupling (Figure 5). [ 108 ]…”

Section: Classical Sonogashira Coupling Reactionsmentioning

confidence: 99%

Recent Expedition inPd‐CatalyzedSonogashira Coupling and Related Processes^†

2023

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Sonogashira cross-coupling protocol, typically showing the reaction between aryl/vinyl halide and terminal alkyne, has been a widely used protocol for constructing C(sp 2 )-C(sp) bond. The resulting internal alkynes are highly versatile for reaching differently functionalized alkyne-containing scaffolds or serving as valuable synthetic synthons to many other functional groups. It is worth noting that products originated from this coupling reaction are mostly applicable to be transformed into corresponding Z-alkene, alkane, or heterocyclic moieties in natural product syntheses. The reaction conditions and catalyst systems are able to be tweaked in order to facilitate the activation of steric hindered and/or electron-rich electrophiles. Pd-catalyzed copper-free Sonogashira coupling reaction has caught increasing attention as the improved method can be more environmentally friendly. What is more, the conditions of the coupling reaction can be readily amended to allow the fusion of other carbonylation or decarboxylation step in the catalytic cycle, and thus allow more complex yet versatile convergent synthesis to proceed in an operationally simple one-pot manner.

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Section: Classical Sonogashira Coupling Reactionsmentioning

confidence: 99%

Recent Expedition inPd‐CatalyzedSonogashira Coupling and Related Processes^†

2023

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“…Our research is focused on the development of sustainable synthetic protocols utilizing heterogeneous catalytic systems − and focusing on the design and development of tailor-made polymeric supports for the preparation of immobilized catalysts with specific stability and versatility. − …”

Section: Introductionmentioning

confidence: 99%

Waste-Minimized Continuous-Flow Synthesis of Oxindoles Exploiting a Polymer-Supported N Heterocyclic Palladium Carbene Complex in a CPME/Water Azeotrope

Salameh

Ferlin

Valentini

et al. 2022

ACS Sustainable Chem. Eng.

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Herein, we report the development of an effective synthetic protocol for the synthesis of oxindoles in flow based on a C(sp 3 )−H activation process promoted by a supported Nheterocyclic carbene palladium heterogeneous catalytic system using cyclopentyl methyl ether (CPME) as the reaction medium. The design of the catalyst, the selection of the solvent medium, and the definition of a tailored continuous flow reactor have been all designed to establish an efficient waste-minimized process for the intramolecular cyclization of N-methyl-2-halo-acetanilides. The use of CPME in its aqueous azeotropic mixture has allowed us to reach high yields of products with a simplified precipitation workup that includes the downstream process separation and recycling of the solvent. An assessment of the environmental and safety hazard features has also been made in order to better clarify the implications in terms of sustainability of the newly developed process.

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“…Metal nanoparticles have become widely interesting for the development of highly effective catalytic systems, exploiting larger surface properties. , However, due to their obvious small size, heterogeneous matrix supports (i.e., silica, − zirconia, , polymers, − and carbon-based supports) − are often required to optimize their use. The major challenge to exploit the high efficiency of palladium nanoparticles is the control of size distribution, which is strictly connected to the catalyst activity.…”

Section: Introductionmentioning

confidence: 99%

Tailor-Made POLITAG-Pd⁰ Catalyst for the Low-Loading Mizoroki–Heck Reaction in γ-Valerolactone as a Safe Reaction Medium

Valentini

Carpisassi

Comès

et al. 2022

ACS Sustainable Chem. Eng.

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In this contribution, we have reported our study on the fine-tuned design and synthesis of new POLITAGs-Pd0 (POLymeric Ionic TAG) catalytic systems with the intention of defining highly efficient heterogeneous palladium catalysts stabilized by ionic tags able to operate at a very low loading while being fully recoverable/reusable. By varying both the support and the ratio between the metal and immobilized ionic tag, we have accessed five different heterogeneous catalytic systems that have been fully characterized (EA, XPS, TEM, and HR-TEM) to investigate their morphological differences. The catalytic efficiency of the newly prepared POLITAGs-Pd0 materials was then tested and compared in the representative Mizoroki–Heck cross-coupling reaction, a universally investigated and widely useful process. A close correlation between the catalyst support and catalytic performances has been highlighted. The best system POLITAG-Pd0-HM features a high TOF value (26,786 h–1), affording the final products in high isolated yields by using as little as only 0.0007 mol % of Pd. Moreover, this high catalytic activity coupled with the use of γ-valerolactone (GVL) as a green reaction medium has led to the definition of a very efficient waste-minimized protocol. The newly designed catalyst has been utilized in the representative synthesis of Amiloxate, a widely used sunscreen agent, that could be prepared with negligible metal contamination and very low E-factor.

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Si-Gly-CD-PdNPs as a hybrid heterogeneous catalyst for environmentally friendly continuous flow Sonogashira cross-coupling

Abstract: We have reported a waste-minimized protocol for the Sonogashira cross-coupling exploiting the safe use of CPME/water azeotropic mixture and the utilization of a heterogeneous hybrid palladium catalyst supported onto silica/β-cyclodextrin...

Cited by 16 publications

References 82 publications

Recent Expedition inPd‐CatalyzedSonogashira Coupling and Related Processes^†

Recent Expedition inPd‐CatalyzedSonogashira Coupling and Related Processes^†

Waste-Minimized Continuous-Flow Synthesis of Oxindoles Exploiting a Polymer-Supported N Heterocyclic Palladium Carbene Complex in a CPME/Water Azeotrope

Tailor-Made POLITAG-Pd⁰ Catalyst for the Low-Loading Mizoroki–Heck Reaction in γ-Valerolactone as a Safe Reaction Medium

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Si-Gly-CD-PdNPs as a hybrid heterogeneous catalyst for environmentally friendly continuous flow Sonogashira cross-coupling

Abstract: We have reported a waste-minimized protocol for the Sonogashira cross-coupling exploiting the safe use of CPME/water azeotropic mixture and the utilization of a heterogeneous hybrid palladium catalyst supported onto silica/β-cyclodextrin...

Cited by 16 publications

References 82 publications

Recent Expedition inPd‐CatalyzedSonogashira Coupling and Related Processes†

Recent Expedition inPd‐CatalyzedSonogashira Coupling and Related Processes†

Waste-Minimized Continuous-Flow Synthesis of Oxindoles Exploiting a Polymer-Supported N Heterocyclic Palladium Carbene Complex in a CPME/Water Azeotrope

Tailor-Made POLITAG-Pd0 Catalyst for the Low-Loading Mizoroki–Heck Reaction in γ-Valerolactone as a Safe Reaction Medium

Contact Info

Product

Resources

About

Recent Expedition inPd‐CatalyzedSonogashira Coupling and Related Processes^†

Recent Expedition inPd‐CatalyzedSonogashira Coupling and Related Processes^†

Tailor-Made POLITAG-Pd⁰ Catalyst for the Low-Loading Mizoroki–Heck Reaction in γ-Valerolactone as a Safe Reaction Medium