Metal Nanoparticles Catalyzed C–C Bond Formation via C–H Activation

Valentini, Federica; Brufani, Giulia; Latterini, Loredana; Vaccaro, Luigi

doi:10.1021/bk-2020-1359.ch017

Cited by 14 publications

(7 citation statements)

References 220 publications

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“…Over the last years, hydrogen isotope exchange (HIE) reactions have attracted much interest due to the increasing importance of isotope-containing molecules in various areas including materials and life sciences, in addition to their established utilization in mechanistic studies in chemistry and biology. , Moreover, C–H activation has become a powerful technique for the synthesis or functionalization of complex organic compounds via the subsequent formation of a large variety of C–C, C–N, C–O, and C–B bonds …”

Section: Introductionmentioning

confidence: 99%

Bringing Selectivity in H/D Exchange Reactions Catalyzed by Metal Nanoparticles through Modulation of the Metal and the Ligand Shell

et al. 2023

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Ru and Rh nanoparticles catalyze the selective H/D exchange in phosphines using D 2 as the deuterium source. The position of the deuterium incorporation is determined by the structure of the P-based substrates, while activity depends on the nature of the metal, the properties of the stabilizing agents, and the type of the substituent on phosphorus. The appropriate catalyst can thus be selected either for the exclusive H/D exchange in aromatic rings or also for alkyl substituents. The selectivity observed in each case provides relevant information on the coordination mode of the ligand. Density functional theory calculations provide insights into the H/D exchange mechanism and reveal a strong influence of the phosphine structure on the selectivity. The isotope exchange proceeds via C−H bond activation at nanoparticle edges. Phosphines with strong coordination through the phosphorus atom such as PPh 3 or PPh 2 Me show preferred deuteration at ortho positions of aromatic rings and at the methyl substituents. This selectivity is observed because the corresponding C−H moieties can interact with the nanoparticle surface while the phosphine is Pcoordinated, and the C−H activation results in stable metallacyclic intermediates. For weakly coordinating phosphines such as P(otolyl) 3 , the interaction with the nanoparticle can occur directly through phosphine substituents, and then, other deuteration patterns are observed.

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Section: Introductionmentioning

confidence: 99%

Bringing Selectivity in H/D Exchange Reactions Catalyzed by Metal Nanoparticles through Modulation of the Metal and the Ligand Shell

et al. 2023

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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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“…In the past two decades, metal nanoparticles (MNPs) have found successful use as catalytic systems to promote a wide range of transformations such as C-C coupling, reduction and oxidation reactions [22][23][24][25][26][27][28][29][30]. More recently, due to their tunable electronic, chemical properties, shape, size and composition, MNPs with a high surface-to-volume ratio have been shown to be very efficient catalyst for the C-H functionalization (C-C, C-Heteroatom) via C-H activation under mild reaction conditions [31][32][33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48][49][50].…”

Section: Introductionmentioning

confidence: 99%

Metal and Metal Oxide Nanoparticles Catalyzed C–H Activation for C–O and C–X (X = Halogen, B, P, S, Se) Bond Formation

2022

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The direct functionalization of an inactivated C–H bond has become an attractive approach to evolve toward step-economy, atom-efficient and environmentally sustainable processes. In this regard, the design and preparation of highly active metal nanoparticles as efficient catalysts for C–H bond activation under mild reaction conditions still continue to be investigated. This review focuses on the functionalization of un-activated C(sp3)–H, C(sp2)–H and C(sp)–H bonds exploiting metal and metal oxide nanoparticles C–H activation for C–O and C–X (X = Halogen, B, P, S, Se) bond formation, resulting in more sustainable access to industrial production.

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Metal Nanoparticles Catalyzed C–C Bond Formation via C–H Activation

Cited by 14 publications

References 220 publications

Bringing Selectivity in H/D Exchange Reactions Catalyzed by Metal Nanoparticles through Modulation of the Metal and the Ligand Shell

Bringing Selectivity in H/D Exchange Reactions Catalyzed by Metal Nanoparticles through Modulation of the Metal and the Ligand Shell

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

Metal and Metal Oxide Nanoparticles Catalyzed C–H Activation for C–O and C–X (X = Halogen, B, P, S, Se) Bond Formation

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Metal Nanoparticles Catalyzed C–C Bond Formation via C–H Activation

Cited by 14 publications

References 220 publications

Bringing Selectivity in H/D Exchange Reactions Catalyzed by Metal Nanoparticles through Modulation of the Metal and the Ligand Shell

Bringing Selectivity in H/D Exchange Reactions Catalyzed by Metal Nanoparticles through Modulation of the Metal and the Ligand Shell

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

Metal and Metal Oxide Nanoparticles Catalyzed C–H Activation for C–O and C–X (X = Halogen, B, P, S, Se) Bond Formation

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