Grignard reagent formation

Garst, John F.; Soriaga, Manuel P.

doi:10.1016/j.ccr.2004.02.018

Cited by 135 publications

(98 citation statements)

References 59 publications

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“…In another report we have shown that with a radical clock bearing an oxygen atom instead of a benzylic CH 2 group (CH 2 replaced with O in (E)-2), high yields of cyclised product are obtained in the formation of Grignard reagent. [35] However, the effect of the phenyl group on the oxygen probe cyclisation rate constant is minor [43] and this more ambiguous [48] increase would deserve further investigation.…”

Section: Resultsmentioning

confidence: 95%

“…Isomerisations in the corresponding Grignard reactions could be artefacts arising through other processes". [48] We discuss this proposition further later; starting from his first sentence explains why we tried other structural modifications on the probes shown in Scheme 1.…”

Section: Entrymentioning

confidence: 97%

“…[74][75][76] This was an original proposition, because up to their work it had been believed that the route from radicals to RMgX involved a direct coupling of radical R · with the paramagnetic MgX · species formed by reaction between Mg radical cations and X anions. [77,78] In Bickelhaupt's and Garst's representations, RMgX results from reactions of R carbanions with MgX + [75] and MgX 2 , [48] respectively. Solvent effects fit with this proposition.…”

Section: Entrymentioning

confidence: 99%

“…[48] The best identified cases of ring-closure reactions triggered by an electron transfer and involving C-C bond formation are intramolecular S RN 1 reactions. These have recently been reviewed.…”

Section: Entrymentioning

confidence: 99%

“…[79] Later, Garst returned to this point and laid stress on polarity factors. [34,48] In this scheme of things, the polarity of the solvent plays a role in the value of k 3 (Scheme 2): more polar solvents increase its value. [80] The higher polarity of THF therefore fits with the lower yield of cyclised products obtained in this solvent: if the cleavage of the radical anion is faster, the aryl radical is created near the surface and has good chances of being reduced more rapidly.…”

Section: Entrymentioning

confidence: 99%

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Structural Effects in Radical Clocks and Mechanisms of Grignard Reagent Formation: Special Effect of a Phenyl Substituent in a Radical Clock when the Crossroads of Selectivity is at a Metal/Solution Interface

et al. 2009

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A large class of radical clocks is based on the intramolecular trapping of a reactive radical by a suitably located unsaturated system. Depending on the substituents present on this unsaturated system, the rate of cyclisation may vary drastically. This property has been repeatedly used to diagnose the participation of very short-lived radicals in the mechanisms of a wide variety of reactions. For reactions occurring in homogeneous solution, a phenyl substituent capable of stabilizing the radical formed during the act of trapping has been one of the most widely used tools of this type. During study of the mechanisms of formation of Grignard reagents -reactions that occur at the interface of the metal and the solution -the phenyl substituent displayed a specific new behaviour pattern. Besides its stabilizing role, it was also able to play the role of mediator in redox catalysis of electron transfer. In this case, the first events on the pathway to the Grignard reagents involve a cascade of three (one intermolecular followed by two intramolecular) electron transfers. Introduction of a p-methoxy substituent on the phenyl ring, making the phenyl group a poorer electron acceptor, suppresses this

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Section: Resultsmentioning

confidence: 95%

Section: Entrymentioning

confidence: 97%

Section: Entrymentioning

confidence: 99%

Section: Entrymentioning

confidence: 99%

Section: Entrymentioning

confidence: 99%

See 3 more Smart Citations

Structural Effects in Radical Clocks and Mechanisms of Grignard Reagent Formation: Special Effect of a Phenyl Substituent in a Radical Clock when the Crossroads of Selectivity is at a Metal/Solution Interface

et al. 2009

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Liquid Salts for Reactions

Johnson

Pagni

2012

Kirk-Othmer Encyclopedia of Chemical Technology

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Organic reactions in room temperature liquid salts have received considerable attention in the last two decades, many of which are highlighted in the short review. Organic reactions occurring in high temperature liquid salts, a topic neglected in the last two decades, are also highlighted. The review will help the interested researcher in choosing a solvent in which to carry out a particular transformation.

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Formation, Chemistry and Structure of Organomagnesium Species in Solvent‐Free Environments

O’Hair

2009

Patai's Chemistry of Functional Groups

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Introduction Formation of Organomagnesium Species in Solvent‐Free Environments Bimolecular Reactions of Organomagnesium Ions in the Gas Phase Unimolecular Reactions of Organomagnesium Ions in the Gas Phase Structures of Organomagnesiums and Magnesium Halides in the Gas Phase Concluding Remarks Acknowledgments

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Grignard reagent formation

Cited by 135 publications

References 59 publications

Structural Effects in Radical Clocks and Mechanisms of Grignard Reagent Formation: Special Effect of a Phenyl Substituent in a Radical Clock when the Crossroads of Selectivity is at a Metal/Solution Interface

Structural Effects in Radical Clocks and Mechanisms of Grignard Reagent Formation: Special Effect of a Phenyl Substituent in a Radical Clock when the Crossroads of Selectivity is at a Metal/Solution Interface

Liquid Salts for Reactions

Formation, Chemistry and Structure of Organomagnesium Species in Solvent‐Free Environments

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