Halide exchanged Hoveyda-type complexes in olefin metathesis

Wappel, Julia; Urbina‐Blanco, César A.; Abbas, Mudassar; Albering, Joerg H.; Saf, Robert; Nolan, Steven P.; Slugovc, Christian

doi:10.3762/bjoc.6.125

Cited by 53 publications

(43 citation statements)

References 32 publications

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“…Methyl oleate (technical grade, *70%, Fluka, consisting of a mixture of derivatives with a chain length distribution of C 12 (1%), C 14 (3%), C 16 (12%), C 18 (83%), and C 20 (1%)), ethyl acrylate (99%, Aldrich, stabilized with 0.002% hydroquinone monoethyl ether), and oleylamine (technical grade, *70%, Aldrich, consisting of a mixture of derivatives with a chain length distribution of C 12 (1%), C 14 (4%), C 16 (13%), C 18 (81%, (E) and (Z)-diastereomers), and C 20 (1%)) were used as received. Catalysts 1 and 3 were prepared in accordance with literature methods [13,20]. Catalyst 2 was received from Umicore.…”

Section: Methodsmentioning

confidence: 99%

Optimized reaction conditions for the cross-metathesis of methyl oleate and oleylamine with ethyl acrylate

Abbas

Slugovc

2012

Monatsh Chem

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The cross-metathesis of methyl oleate and oleylamine with ethyl acrylate has been studied using three different ruthenium-based second-generation catalysts. Emphasis was on determining the smallest amount of catalyst necessary for full conversion of technical grade educts. Conversion of methyl oleate is best performed in the presence of 10 equiv. ethyl acrylate without use of additional solvent whereas oleylamine cannot be used directly and protection of the amino group is necessary. An easy protection procedure for oleylamine with acetic anhydride was developed and the best results for crossmetathesis of N-acetyloleylamine were obtained in toluene solution.

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Section: Methodsmentioning

confidence: 99%

Optimized reaction conditions for the cross-metathesis of methyl oleate and oleylamine with ethyl acrylate

Abbas

Slugovc

2012

Monatsh Chem

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“…The search for new improved catalysts for ruthenium metathesis focused mainly on the modifications of alkylidene ligand or the L 2 units in [L 2 X 2 Ru=CHR] scaffold characteristic of the family of Grubbs catalyst has made considerable progress and led to development of new generations of catalysts 1a. 2 Increasing number of reports is also observed on exchange of anionic ligands, in particular parent chloride ligands with other halides,3a,b alkoxides,3c aryloxides,3d–g carboxylates including perfluorocarboxylates,3h–o diketonates,3p isocyanates (OCN − ),3l,q isothiocyanates (SCN − ),3l,q sulphonates,3e,j,r,s phosphonates,3r and nitrate 3l,t. Several accounts report application of chelating carboxylates,4a–e alkoxides and aryloxides3t, 4f–g including Schiff bases 4h,i.…”

Section: Methodsmentioning

confidence: 99%

Ruthenium–Amido Complexes: Synthesis, Structure, and Catalytic Activity in Olefin Metathesis

Pietraszuk¹,

Rogalski²,

Powała³

et al. 2012

Chemistry A European J

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Unprecedented amido derivatives of the first‐, second‐, and third‐generation Grubbs ruthenium catalysts were prepared, characterized, and tested in ring‐closing metathesis (RCM) of model dienes. In the ruthenium–amide (formally: 2‐ruthenaindole) form, these complexes exhibit nearly no activity in RCM. However, a dramatic increase of activity was observed upon in situ activation with an ethereal solution of HCl (see figure).

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“…This observed superior latent behavior of catalysts bearing iodide ligands compared to chloride ligands is consistent with previously reported reactivity trends for catalysts with different halogen ligands. 28 …”

Section: Resultsmentioning

confidence: 99%

Thermally Stable, Latent Olefin Metathesis Catalysts

et al. 2011

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Highly thermally stable N-aryl,N-alkyl N-heterocyclic carbene (NHC) ruthenium catalysts were designed and synthesized for latent olefin metathesis. These catalysts showed excellent latent behavior toward metathesis reactions, whereby the complexes were inactive at ambient temperature and initiated at elevated temperatures, a challenging property to achieve with second generation catalysts. A sterically hindered N-tert-butyl substituent on the NHC ligand of the ruthenium complex was found to induce latent behavior toward cross-metathesis reactions, and exchange of the chloride ligands for iodide ligands was necessary to attain latent behavior during ring-opening metathesis polymerization (ROMP). Iodide-based catalysts showed no reactivity toward ROMP of norbornene-derived monomers at 25 °C, and upon heating to 85 °C gave complete conversion of monomer to polymer in less than 2 hours. All of the complexes were very stable to air, moisture, and elevated temperatures up to at least 90 °C, and exhibited a long catalyst lifetime in solution at elevated temperatures.

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Halide exchanged Hoveyda-type complexes in olefin metathesis

Cited by 53 publications

References 32 publications

Optimized reaction conditions for the cross-metathesis of methyl oleate and oleylamine with ethyl acrylate

Optimized reaction conditions for the cross-metathesis of methyl oleate and oleylamine with ethyl acrylate

Ruthenium–Amido Complexes: Synthesis, Structure, and Catalytic Activity in Olefin Metathesis

Thermally Stable, Latent Olefin Metathesis Catalysts

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