Double CH Activation of an N‐Heterocyclic Carbene Ligand in a Ruthenium Olefin Metathesis Catalyst

Hong, Soon Hyeok; Chlenov, Anatoly; Day, Michael; Grubbs, Robert H.

doi:10.1002/anie.200701234

Cited by 144 publications

(75 citation statements)

References 20 publications

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“…Therefore, we suggest that 8 suffers from a tendency to undergo ortho metallation with the 2-hydroxyphenyl amino side group. [46,[56][57][58] Scheme 3. Losing the chelate effect.…”

Section: Resultsmentioning

confidence: 99%

Ruthenium‐Based NHC‐Arene Systems as Ring‐Opening Metathesis Polymerisation Catalysts

2007

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The availability of starting materials, the complexity of the preparative routes and the cost to make the catalyst are key in the development of industrially relevant olefin metathesis catalysts. With this in mind, new synthetic routes, which lead to alternatives for the classic ruthenium benzylidene complexes and circumvent the need for patented Grubbs intermediates were explored. The research presented herein focuses on the coordination of "saturated" N-heterocyclic carbene (NHC) ligands to Ru dimer [(p-cymene)RuCl 2 ] 2 . As the coordination of the standard NHC ligand H 2 IMes (1,3-dimes-

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“…Therefore, we suggest that 8 suffers from a tendency to undergo ortho metallation with the 2-hydroxyphenyl amino side group. [46,[56][57][58] Scheme 3. Losing the chelate effect.…”

Section: Resultsmentioning

confidence: 99%

Ruthenium‐Based NHC‐Arene Systems as Ring‐Opening Metathesis Polymerisation Catalysts

2007

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“…In a later study on the highly unstable N‐heterocyclic Ru‐methylidene complex 3 , a key intermediate in the metathesis reaction of catalyst 2 , a dinuclear Ru carbide hydride species was successfully isolated and two possible mechanisms, involving intermolecular and intramolecular phosphine attack on the Ru‐carbene, were proposed (Scheme ) . In addition, the C–H activation products from the unstable N‐heterocyclic carbene‐based catalyst 4 were found in their subsequent studies . Diver and co‐workers reported carbon monoxide‐ or isocyanide‐promoted ylidene transfer rearrangement in the 1 st and 2 nd Grubbs catalysts 1 and 2 .…”

Section: Methodsmentioning

confidence: 98%

Studies on CH₃CN‐assisted decomposition of 1^st Grubbs catalyst by electrospray ionization tandem mass spectrometry

Zhao

Wang

Guo

2011

Rapid Comm Mass Spectrometry

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The CH(3)CN-assisted decomposition reaction of the 1(st) Grubbs catalyst (1) was studied using electrospray ionization tandem mass spectrometry (ESI-MS/MS). We detected a series of Ru-intermediates and decomposition products by off-line and on-line ESI-MS(/MS) monitoring of the decomposition process. In particular, an on-line microreactor method was applied with ESI-MS/MS to profile the change and relationship of various Ru-intermediates by controlling the reaction within the first 30 s of its time scale. The main fast decomposition mechanism of Ru-catalyst 1 in the presence of CH(3)CN was similar to that proposed by Grubbs, and this was confirmed by detecting the (PhCH(2)PCy(3))(+) ion at m/z 371 as the major decomposition products with ESI-MS. We also studied the time evolution of the transient reactive Ru-intermediate ions step by step with ESI-MS/MS and detected the C-H bond activation products of toluene--dehydrogenated PCy(3), such as P(Cy)(2)(C(6)H(9)), P(Cy)(2)Ph--by analyzing the decomposition reaction solution by gas chromatography (GC)/MS. The mechanism of another minor decomposition pathway involving the phosphine activation of catalyst 1 was proposed on the basis of the ESI-MS(/MS) interception and characterization of the transient reactive Ru-species in the decomposition reaction solution. Finally the coordination effect of the CH(3)CN in assisting the decomposition and stabilizing the transient Ru-complexes is discussed.

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“…It remains to be seen whether this useful reaction can be applied in the context of proteins under physiological conditions. The new generation of water-compatible rutheniumbased catalysts [68] combined with the ability to introduce unnatural functionalities into proteins (e.g., alkene), using synthetic and biochemical approaches, [8] encourages us to suggest that such a goal might not be far from our reach.…”

Section: Metathesis In Miscellaneous Peptidic Systemsmentioning

confidence: 98%

Metathesis in Peptides and Peptidomimetics

Brik

2008

Adv Synth Catal

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This review is intended to cover the applications of olefin metathesis, with its variations, to the synthesis and manipulation of peptides and peptidomimetics. The examples presented here emphasize the use of metathesis in several aspects of peptides and peptidomimetics, from amino acid synthesis, design and synthesis of secondary structure elements, and manipulation of pharmaceutically active peptides and peptidomimetics to improve their stability and activity. These examples testify to the power of the ruthenium-based catalysts, which are particularly useful in the synthesis of complex molecules such as peptides, due to their high stability in various media, high chemoselectivity, and tolerance to a variety of functional groups that decorate the peptide side chains. Another observation one could make from surveying these studies is that ring-closing metathesis (RCM) is the most used variation of olefin metathesis in these fields. Finally, metathesis, which leads to the formation of carbon-carbon bonds with various hybridization states, i.e., alkyne, alkene, and alkane allows for great diversity and flexibility in the synthesis leading to novel structures and function properties. Unarguably, metathesis is a fascinating reaction that continues to have its impact in various fields including peptides and peptidomimetics.

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Double CH Activation of an N‐Heterocyclic Carbene Ligand in a Ruthenium Olefin Metathesis Catalyst

Cited by 144 publications

References 20 publications

Ruthenium‐Based NHC‐Arene Systems as Ring‐Opening Metathesis Polymerisation Catalysts

Ruthenium‐Based NHC‐Arene Systems as Ring‐Opening Metathesis Polymerisation Catalysts

Studies on CH₃CN‐assisted decomposition of 1^st Grubbs catalyst by electrospray ionization tandem mass spectrometry

Metathesis in Peptides and Peptidomimetics

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Double CH Activation of an N‐Heterocyclic Carbene Ligand in a Ruthenium Olefin Metathesis Catalyst

Cited by 144 publications

References 20 publications

Ruthenium‐Based NHC‐Arene Systems as Ring‐Opening Metathesis Polymerisation Catalysts

Ruthenium‐Based NHC‐Arene Systems as Ring‐Opening Metathesis Polymerisation Catalysts

Studies on CH3CN‐assisted decomposition of 1st Grubbs catalyst by electrospray ionization tandem mass spectrometry

Metathesis in Peptides and Peptidomimetics

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Studies on CH₃CN‐assisted decomposition of 1^st Grubbs catalyst by electrospray ionization tandem mass spectrometry