Industrial R&amp;D on Catalytic CC and CN Coupling Reactions: A Personal Account on Goals, Approaches and Results

Blaser, Hans‐Ulrich; Indolese, Adriano F.; Naud, Frédéric; Nettekoven, Ulrike; Schnyder, Anita

doi:10.1002/adsc.200404156

Cited by 216 publications

(103 citation statements)

References 53 publications

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“…The polymerization was monitored by NMR spectroscopy. After the polymerization was complete as determined by 1 H NMR, a few drops of ethyl vinyl ether were added to terminate the polymerization. The polymer was purified by repeated precipitations into cold methanol followed by centrifugation at 400 rpm for ten minutes.…”

Section: General Polymerization Procedures For the Synthesis Of Polymementioning

confidence: 99%

Poly(norbornene)‐Supported N‐Heterocyclic Carbenes as Ligands in Catalysis

Sommer

Weck

2006

Adv Synth Catal

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In this contribution, we present the synthesis of norbornene-supported N-heterocyclic (NHC) carbenes. These functionalized norbornenes were polymerized via ring-opening metathesis polymerization in a controlled fashion either before or after metalation with a variety of palladium and ruthenium precursors resulting in the formation of polymersupported NHC-based metal catalysts. The activities of the palladium-based catalysts in the SuzukiMiyaura, Sonogashira and Heck coupling reactions were studied in detail. In all cases, the polymeric catalysts demonstrated the same activity as their small molecule analogues. Furthermore, we carried out preliminary investigations into the stability of these catalysts using poisoning studies. A clear dependence of the stability of the polymer-supported catalysts on their palladium precursor was observed with palladium acetate-based polymeric NHC catalysts being the most stable. Finally, we have studied the reactivity of our supported NHC ruthenium complexes as catalysts for ring-closing metathesis. Again, in all cases good conversions were observed with comparable activities to other supported NHC-ruthenium catalysts. Lastly, we were able to remove the ruthenium catalysts from the solution quantitatively demonstrating the possibility of metal removal.

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Section: General Polymerization Procedures For the Synthesis Of Polymementioning

confidence: 99%

Poly(norbornene)‐Supported N‐Heterocyclic Carbenes as Ligands in Catalysis

Sommer

Weck

2006

Adv Synth Catal

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“…[1] This steadily growing importance is due to the mild conditions associated with their use, making them compatible with a wide variety of functional groups.…”

Section: Introductionmentioning

confidence: 99%

Use of “Homeopathic” Ligand‐Free Palladium as Catalyst for Aryl‐Aryl Coupling Reactions

et al. 2004

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Abstract:We have previously shown that the use of ligand-free palladium employing Pd(OAc) 2 as catalyst precursor in the Heck reaction of aryl bromides is possible if low catalyst loadings, typically between 0.01 -0.1 mol % are used. We have now tested this phenomenon, which we have dubbed "homeopathic" palladium, in biaryl formation using the Suzuki, the Negishi and the Kumada cross-coupling reactions. The Suzuki reaction of aryl bromides, both activated and deactivated, is possible using 0.02 -0.05 mol % of Pd(OAc) 2 . In this reaction turnover frequencies up to 30,000 have been reached with activated substrates. Even aryl chlorides could be reacted if strongly electron-withdrawing substituents were present. The Negishi coupling with a variety of arylzinc halides was possible on aryl bromides containing electronwithdrawing substituents. The Kumada reaction only gave low yields of products under "homeopathic conditions.

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“…Transition-metal-based catalysis has been a corner stone for the synthesis of specialty chemicals for diverse applications ranging from materials to pharmaceuticals [13]. The design of transition metal catalysts has to take into account several basic characteristics, including high efficiencies and selectivity, as well as economic and environmental considerations.…”

Section: Introductionmentioning

confidence: 99%

Polyimide-Supported Dichloro-1,3-bis(p-dimethylaminobenzyl)benzimidazolidin-2-ilidenruthenium (II) as Effective Catalyst for Hydrosilylation Reactions

Köytepe

Seçki̇n

Yaşar

et al. 2008

Designed Monomers and Polymers

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The present study relates to a heterogeneous polyimide-supported transition metal complex catalyst for hydrosilylation reactions, which is prepared by functionalizing a heat-and acid-resistant polyimide resin with a homogeneous metal catalyst of ruthenium (II) complex. The heterogeneous polyimide-supported transition metal complex catalyst of the invention provides superior catalytic activity, selectivity and stability in the hydrosilylation of acetophenone. Further, the catalyst has strong resistance against heat and acid. Besides, the catalyst of the invention may provide the following advantage which are critical in industrial use: it can be easily separated from the reaction product, which eases recycling of the catalyst.

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Industrial R&D on Catalytic CC and CN Coupling Reactions: A Personal Account on Goals, Approaches and Results

Cited by 216 publications

References 53 publications

Poly(norbornene)‐Supported N‐Heterocyclic Carbenes as Ligands in Catalysis

Poly(norbornene)‐Supported N‐Heterocyclic Carbenes as Ligands in Catalysis

Use of “Homeopathic” Ligand‐Free Palladium as Catalyst for Aryl‐Aryl Coupling Reactions

Polyimide-Supported Dichloro-1,3-bis(p-dimethylaminobenzyl)benzimidazolidin-2-ilidenruthenium (II) as Effective Catalyst for Hydrosilylation Reactions

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