Recent advances in the synthesis of supported metathesis catalysts

Buchmeiser, Michael R.

doi:10.1039/b315236g

Cited by 134 publications

(44 citation statements)

References 93 publications

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“…[3,41] Connon and Blechert synthesized the phosphine-free ruthenium alkylidene 53 bound to the hydrophilic solid support PEGA-NH 2 (PEGA = poly(ethylene glycol)-acrylamide copolymer). This heterogeneous catalyst was much less sensitive towards oxygen and promoted various RCM and CM reactions in nondegassed methanol and in water (Table 1).…”

Section: Ruthenium Complexes Bound To Hydrophilic Polymersmentioning

confidence: 99%

Aqueous Olefin Metathesis

2008

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According to popular belief, oxygen and water are the natural enemies of organometallic reactions and therefore must be excluded rigorously from the reaction vessel. This belief is founded in the case of the highly reactive nucleophilic metal alkylidene complexes that were used in early catalytic olefin metathesis. However, owing to the high stability of the ruthenium carbene complexes introduced by Grubbs, metathesis in water has become reality.

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Section: Ruthenium Complexes Bound To Hydrophilic Polymersmentioning

confidence: 99%

Aqueous Olefin Metathesis

2008

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“…In metathesis reactions, the latter is often restricted by the instability of intermediate transition metal methylidenes. While a comparably large number of supported ruthenium-based Grubbs-and Grubbs-Hoveyda-type metathesis catalysts are already available, [10][11][12] there exists still an only very limited number of supported Schrock-type catalysts. [6] In this context, surface-located transition metal carbenes have been reported to possess metathesis activity.…”

Section: Introductionmentioning

confidence: 99%

Polymer‐Supported Chiral Schrock Catalysts Immobilized via the Arylimido Ligand

et al. 2006

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The immobilization of both chiral and non-chiral versions of the Schrock catalyst via the arylimido ligand was accomplished for the first time. For this purpose, four different 4-(6-halogenohexyl)-2,6-R 2 -anilines, i.e., {4-[6-X-(CH 2 ) 6 ]-2,6-R 2 -C 6 H 2 -NH 2 } (7: R= Me, X = Br; 8: R= Me, X = Cl, 9: R= 2-Pr, X = Cl, 10: R= 2-Pr, X = Br) were prepared and used for the synthesis of the corresponding MobisA C H T U N G T R E N N U N G (imido)dichloro complexes Mo{N-2,6-R 2 -4-[6-X-(CH 2 ) 6 ]-C 6 H 2 } 2 Cl 2 ·DME (11: R= Me, X = Br; 12: R = Me, X = Cl; 13: R= 2-Pr, X = Cl; 14: R= 2-Pr, X = Br). Compounds 11-14 were transformed into the corresponding Mo-bisA C H T U N G T R E N N U N G (imido)dialkyl complexes Mo{N-2,6-R 2 -4-[6-X-(CH 2 ) 6 ]-C 6 H 2 } 2 (CH 2 CMe 2 Ph) 2 (15: R= Me, X = Br; 16: R= Me, X = Cl, 17: R= 2-Pr, X = Cl; 18: R= 2-Pr, X = Br). These were used for the synthesis of the Mo-imidoalkylidene triflates·DME (19: R= Me, X = Br; 20: R= 2-Pr, X = Br, 21: R= 2-Pr, X = Cl). Compounds 19--21 were used in the synthesis of the Schrock type catalysts H T U N G T R E N N U N G (CHCMe 2 Ph)[OC-A C H T U N G T R E N N U N G (CH 3 )A C H T U N G T R E N N U N G (CF 3 ) 2 ] (23), Mo{N-2,6-Me 2 -4-[6-Br-(CH 2 ) 6 ]-C 6 H 2 }A C H T U N G T R E N N U N G (CHCMe 2 Ph)[(R)-BIPHEN] (24) and MoA C H T U N G T R E N N U N G {N-2,6-A C H T U N G T R E N N U N G (2-Pr) 2 -4-[6-Br-(CH 2 ) 6 ]-C 6 H 2 }A C H T U N G T R E N N U N G (CHCMe 2 Ph)[(R)-BIPHEN] (25). Compounds 22, 24and 25 were immobilized on Ag-perfluoroalkylsulfonate-modified PS-and PS-DVB materials to yield the corresponding immobilized catalysts Mo{N-2,6-Me 2 -4-28). These were used in a series of ring-closing metathesis (RCM), ringopening cross metathesis, asymmetric RCM and desymmetrization reactions. The use of 27 and 28 resulted in values for enantiomeric excess (ee) virtually identical to those obtained with the corresponding homogeneous chiral catalysts.

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“…Up to now, different approaches have been developed in the heterogenization of this kind of catalysts in organic materials. [2] Earlier attempts by Grubbs and Nguyen to prepare polystyrene-supported catalyst 1 (see Scheme 1) achieved only limited success; it was found to be less reactive than the homogeneous one. [3] Barrett and co-workers immobilized the catalyst on vinyl polystyrene, 2, but recycling and reuse of it cause a dramatic decrease in activity.…”

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confidence: 98%

A Highly Active and Reusable Heterogeneous Ruthenium Catalyst for Olefin Metathesis

Shi

2005

Adv Synth Catal

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Abstract:The synthesis and characterization of Ru complexes of the type [L 2 X 2 Ru ¼ CHR] (L ¼ PPh 3 , PCy 3 , N-heterocyclic carbenes or their derivates; X ¼ Cl) grafted on mesoporous SBA-15 material are described. In this heterogeneous catalyst the Ru complexes are anchored in the pore channels of mesoporous silica material SBA-15 to prevent the decomposition of the catalytic species. Compared with formal organic-supported heterogeneous catalysts, this heterogeneous catalyst shows relatively high catalytic activity in olefin metathesis reactions and can be used several times without any decrease in catalytic activities.

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Recent advances in the synthesis of supported metathesis catalysts

Cited by 134 publications

References 93 publications

Aqueous Olefin Metathesis

Aqueous Olefin Metathesis

Polymer‐Supported Chiral Schrock Catalysts Immobilized via the Arylimido Ligand

A Highly Active and Reusable Heterogeneous Ruthenium Catalyst for Olefin Metathesis

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