Intramolecular metathesis versus Kharasch reactions using the Grubbs metathesis catalyst: towards catalyst economy

Faulkner, James; Edlin, Chris D.; Fengas, David; Preece, Ian; Quayle, Peter; Richards, Stuart N.

doi:10.1016/j.tetlet.2005.02.060

Cited by 44 publications

(15 citation statements)

References 21 publications

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“…For example, Quayle and co-workers have studied the ability and the reaction conditions of the first generation of Grubbs' catalyst to promote either ring closing metathesis (RCM) or ATRC reactions. [28] Demonceau and coworkers reported that the exchange of tricyclohexylphosphine [RuCl2(p-cymene)(PCy3)] with p-substituted triarylphosphine ligands enhanced the catalytic activity of these complexes for the ATRA of carbon tetrachloride to unactivated -olefins. [29] In addition, the reactivity was improved by microwave irradiation.…”

Section: Ruthenium-based Catalystmentioning

confidence: 99%

Atom Transfer Radical Reactions as a Tool for Olefin Functionalization – On the Way to Practical Applications

2011

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Transition‐metal‐catalyzed atom transfer radical reactions of halogenated compounds with olefins constitute a versatile tool in organic synthesis within the area of C–C bond forming transformations. The inter‐ or intramolecular versions, atom transfer radical addition (ATRA) or cyclization (ATRC), respectively, lead to the atom‐economic, useful synthesis of compounds that can be further functionalized. This contribution summarizes the recent developments in this area in terms of catalyst design as well as the applicability of this methodology in sequential, domino, or tandem reactions.

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Section: Ruthenium-based Catalystmentioning

confidence: 99%

Atom Transfer Radical Reactions as a Tool for Olefin Functionalization – On the Way to Practical Applications

2011

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“…[3][4][5][6][7][8][9][10][11][12][13][14] Well-defined ruthenium benzylidene complexes, commonly used as olefin metathesis catalysts, have also been reported to catalyze ATRA and ATRP. 9,[15][16][17][18][19] The ability of ruthenium benzylidene complexes to promote two reactions with such markedly different mechanisms has been utilized in various tandem reactions in which olefin metathesis and ATR reactions take place in one pot. [20][21][22] Generally speaking, tandem catalysts, which catalyze multiple distinct reactions in one pot, are attractive synthetic tools that can simplify reaction procedures and reduce operational costs.…”

Section: Introductionmentioning

confidence: 99%

In Situ Catalyst Modification in Atom Transfer Radical Reactions with Ruthenium Benzylidene Complexes

et al. 2016

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Ruthenium benzylidene complexes are well known as olefin metathesis catalysts. Several reports have demonstrated the ability of these catalysts to also facilitate atom transfer radical (ATR) reactions, such as atom transfer radical addition (ATRA) and atom transfer radical polymerization (ATRP). However, while the mechanism of olefin metathesis with ruthenium benzylidenes has been well-studied, the mechanism by which ruthenium benzylidenes promote ATR reactions remains unknown. To probe this question, we have analyzed seven different ruthenium benzylidene complexes for ATR reactivity. Kinetic studies by 1 H NMR revealed that ruthenium benzylidene complexes are rapidly converted into new ATRA-active, metathesis-inactive species under typical ATRA conditions. When ruthenium benzylidene complexes were activated prior to substrate addition, the resulting activated species exhibited enhanced kinetic reactivity in ATRA with no significant difference in overall product yield compared to the original complexes. Even at low temperature, where the original intact complexes did not catalyze the reaction, pre-activated catalysts successfully reacted. Only the ruthenium benzylidene complexes that could be rapidly transformed into ATRA-active species could successfully catalyze ATRP, whereas other complexes preferred redox-initiated free radical polymerization. Kinetic measurements along with additional mechanistic and computational studies show that a metathesis-inactive ruthenium species, generated in situ from the ruthenium benzylidene complexes is the active catalyst in ATR reactions. Based on data from 1 H, 13 C, and 31 P NMR spectroscopy, and X-ray crystallography, we suspect that this ATRA-active species is a RuxCly(PCy3)z complex.

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“…The obvious advantage would be that the number of expensive or less conveniently available precatalysts required in an organic synthesis laboratory could be significantly reduced, a principle that has recently been described as "catalyst economy" by Quayle and co-workers [32]. Starting point and inspiration of our investigation on this field was the unexpected result described in Scheme 1.…”

Section: Selective Metathesis Versus Non-metathesis Conversion Using mentioning

confidence: 99%

Olefin metathesis and isomerization: From undesired side reactions to useful synthetic methodology

Schmidt

2006

Journal of Molecular Catalysis A: Chemical

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Intramolecular metathesis versus Kharasch reactions using the Grubbs metathesis catalyst: towards catalyst economy

Cited by 44 publications

References 21 publications

Atom Transfer Radical Reactions as a Tool for Olefin Functionalization – On the Way to Practical Applications

Atom Transfer Radical Reactions as a Tool for Olefin Functionalization – On the Way to Practical Applications

In Situ Catalyst Modification in Atom Transfer Radical Reactions with Ruthenium Benzylidene Complexes

Olefin metathesis and isomerization: From undesired side reactions to useful synthetic methodology

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