Recoverable low fluorine content palladium complex-catalyzed Suzuki-Miyaura and Sonogashira coupling reactions under thermomorphic mode

Tessema, Eskedar; Fan, Yuyang; Chiu, Chiao-Fan; Elakkat, Vijayanath; Rahayu, Hening Asti; Shen, Chia–Rui; Karthik, C.S.; Zhang, Peng; Lu, Norman

doi:10.1016/j.tet.2022.132961

Cited by 6 publications

(6 citation statements)

References 60 publications

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“…S27–S51 and Table S1 ). Besides achieving the C–C coupling reactions in water by using these micelles, the catalyst loadings employed is very low compared to other Pd-catalysts ( 32 – 34 ) and other Pd-catalysed carbon–carbon coupling reactions in water ( 35 , 36 ). We have used 0.1 mol% (based on the Pd content) of these micellar solutions for catalyzing these cross-coupling reactions.…”

Section: Resultsmentioning

confidence: 99%

Micellar catalysis: Polymer bound palladium catalyst for carbon-carbon coupling reactions in water

Sengoden,

Bhat,

Rutledge

et al. 2023

Proc. Natl. Acad. Sci. U.S.A.

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Metallosurfactants, defined here as hydrophobic metal-containing groups embedded in hydrophilic units when dispersed in water, emanate in the formation of metallomicelles. This approach continues to attract great interest for its ability to serve as micellar catalysts for various metal-mediated chemical transformations in water. Indeed, relevant to green chemistry, micellar catalysis plays a preeminent function as a replacement for organic solvents in a variety of chemical reactions. There are several methods for the interaction of metal complexes (catalysts or catalyst precursors) and surfactants for producing micellar aggregates. A very effective manner for achieving this involves the direct bonding of the metal center to the amphiphilic polymeric materials. Herein, we describe the synthesis of a metallosurfactant containing a palladium complex covalently incorporated into a CO 2 -based triblock polycarbonate derived using a dicarboxylic acid chain-transfer agent. This amphiphilic polycarbonate was shown to self-assemble in water to provide uniform and spherical micelles, where the catalytic metal center is located in the hydrophobic portion of the micelle. The resulting metallosurfactant was demonstrated to effectively catalyze carbon–carbon coupling reactions at very low catalyst loadings.

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Section: Resultsmentioning

confidence: 99%

Micellar catalysis: Polymer bound palladium catalyst for carbon-carbon coupling reactions in water

Sengoden,

Bhat,

Rutledge

et al. 2023

Proc. Natl. Acad. Sci. U.S.A.

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“…The reported thermomorphic procedures for the HCS coupling are carried at T > 100 °C with aryl iodides and bromides as nonsustainable solvents. 47,48 The recycling procedure is ideal for products sensitive to temperature. 36 In fact, if the reaction was carried out using low palladium loading, the reaction time consistently increased (see Table 3).…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…A solution of 2a in toluene or IBA was added over 3 h to the reaction mixture and after cooling to room temperature 3a was easily recovered by phase separation and the catalyst was recycled (see entries 12 and 13 and Figure b). The reported thermomorphic procedures for the HCS coupling are carried at T > 100 °C with aryl iodides and bromides as nonsustainable solvents. , …”

Section: Resultsmentioning

confidence: 99%

Copper-Free Heck–Cassar–Sonogashira and Suzuki–Miyaura Reactions of Aryl Chlorides: A Sustainable Approach

Palladino,

Fantoni,

Ferrazzano

et al. 2023

ACS Sustainable Chem. Eng.

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Sustainable and efficient aryl halides with copperfree Heck−Cassar−Sonogashira (HCS) and Suzuki−Miyaura (SM) cross-coupling reactions were described. Independently from the aryl chloride substituents, the green protocol based on N-hydroxyethylpyrrolidone (HEP)/water as solvents and sodium 2′-dicyclohexylphosphino-2,6-dimethoxy-1,1′-biphenyl-3-sulfonate (sSPhos) as ligand afforded the target products with a high turnover number (TON), high reaction mass efficiency (RME), and low process mass intensity (PMI). The best results have been obtained with TMG and Cs 2 CO 3 as the base for the HCS and Cs 2 CO 3 and K 2 CO 3 for the SM coupling. The PMI and RME achieved are among the best in the field and allowed us to simplify purification processes that are critical for industrial applications.

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“…Sometimes, the intrinsic properties of catalysts can enable the separation of the catalyst from the rest of the medium without the necessity to add an extractant. Tessema et al [ 81 ] synthesized a palladium-based complex [PdCl 2 [5,5′-bis-(R f CH 2 OCH 2 )-2,2′-bpy] and used it for Suzuki and Sonogashira cross couplings. This specific catalyst had thermomorphic properties and it was thus homogeneous at 140–145 °C during the reactions and became a heterogeneous catalyst when the media was cooled down.…”

Section: Treatment Processes For Rare Metal Recoverymentioning

confidence: 99%

“…The only way to reach a homogeneous catalyst recycling seems to be case specific [ 80 , 81 ]. Some examples of liquid–liquid extractions without the addition of a chelating agent can be found in the literature.…”

Section: Treatment Processes For Rare Metal Recoverymentioning

confidence: 99%

Recovery of Homogeneous Platinoid Catalysts from Pharmaceutical Media: Review on the Existing Treatments and the Perspectives of Membrane Processes

Magne,

Carretier,

Ubiera Ruiz

et al. 2023

Membranes

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Catalyst recovery is a major challenge for reaching the objectives of green chemistry for industry. Indeed, catalysts enable quick and selective syntheses with high reaction yields. This is especially the case for homogeneous platinoid catalysts which are almost indispensable for cross-coupling reactions often used by the pharmaceutical industry. However, they are based on scarce, expensive, and toxic resources. In addition, they are quite sensitive and degrade over time at the end of the reaction. Once degraded, their regeneration is complex and hazardous to implement. Working on their recovery could lead to highly effective catalytic chemistries while limiting the environmental and economic impacts of their one-time uses. This review aims to describe and compare conventional processes for metal removal while discussing their advantages and drawbacks considering the objective of homogeneous catalyst recovery. Most of them lead to difficulty recycling active catalysts due to their ability to only treat metal ions or to chelate catalysts without the possibility to reverse the mechanism. However, membrane processes seem to offer some perspectives with limiting degradations. While membranes are not systematically the best option for recycling homogeneous catalysts, current development might help improve the separation between pharmaceutical active ingredients and catalysts and enable their recycling.

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Recoverable low fluorine content palladium complex-catalyzed Suzuki-Miyaura and Sonogashira coupling reactions under thermomorphic mode

Cited by 6 publications

References 60 publications

Micellar catalysis: Polymer bound palladium catalyst for carbon-carbon coupling reactions in water

Micellar catalysis: Polymer bound palladium catalyst for carbon-carbon coupling reactions in water

Copper-Free Heck–Cassar–Sonogashira and Suzuki–Miyaura Reactions of Aryl Chlorides: A Sustainable Approach

Recovery of Homogeneous Platinoid Catalysts from Pharmaceutical Media: Review on the Existing Treatments and the Perspectives of Membrane Processes

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