The Grignard Reagent Formation Reaction of 2‐Chloro‐1,1,1‐triphenylethane Revisited

Bickelhaupt, F. Matthias; Newcomb, Martin; DeZutter, Christopher B.; Boer, Henk J. R. de

doi:10.1002/ejoc.200800790

Cited by 8 publications

(3 citation statements)

References 51 publications

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“…No cyclized product 6 was formed (<1%). In a series of works, Bickelhaupt's group showed [45][46][47][48] that the reaction of aryl halides with magnesium involves reactive aryl carbanion intermediates whose presence is evidenced by well identified by-products formed in yields of 4-85%. The detailed interpretation of these results involves an aryl bromide radical anion whose cleavage provides an aryl radical which is reduced extremely rapidly into a carbanion.…”

Section: Methodsmentioning

confidence: 99%

Clear-cut difference in the rearrangement of 1-bromo-2-(2-phenyl-3-butenyl)benzene under anionic or radical conditions

Reynaud¹,

Hazimeh²,

Mattalia³

et al. 2011

Arkivoc

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The o-(3-butenyl)phenyl system bearing a phenyl group on the 2-position of the side chain was studied as a potential mechanistic probe for distinguishing between radical and carbanion intermediates. The Bu3SnH reduction of 1-bromo-2-(2-phenyl-3-butenyl)benzene, 4, yields mainly the 1,5-cyclization product, 6, with a preference for the trans-isomer. Treatment of 4 with Mg or t-BuLi leads to double-bond isomerization and yields (E)-1,2-diphenyl-2-butene, 8, along with 3,4-diphenyl-1-butene, 5.

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Section: Methodsmentioning

confidence: 99%

Clear-cut difference in the rearrangement of 1-bromo-2-(2-phenyl-3-butenyl)benzene under anionic or radical conditions

Reynaud¹,

Hazimeh²,

Mattalia³

et al. 2011

Arkivoc

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“…This group proposed that the best way to explain their experimental results for aryl halides was to assume that aryl radicals were reduced to carbanions. [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.…”

Section: Entrymentioning

confidence: 96%

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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“…This radical clock was used by de Boer and co-workers to examine whether radicals were involved in formation of a Grignard reagent from 2-chloro-1,1,1-triphenylethane. 63 Scheme 29…”

Section: Multistep (Cascading) Rearrangementsmentioning

confidence: 99%

Reaction mechanisms : Part (i) Radical and radical ion reactions

Tanko¹

2009

Annu. Rep. Prog. Chem., Sect. B: Org. Chem.

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This chapter examines the major advances in the area of radical and radical ion chemistry from a mechanistic perspective. Fundamental classes of radical/radical ion processes are presented (substitution and atom transfer, addition, and fragmentation). Multi-step (cascading) radical process are discussed, followed by a short section describing several fascinating examples of how Nature uses radical chemistry.

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The Grignard Reagent Formation Reaction of 2‐Chloro‐1,1,1‐triphenylethane Revisited

Cited by 8 publications

References 51 publications

Clear-cut difference in the rearrangement of 1-bromo-2-(2-phenyl-3-butenyl)benzene under anionic or radical conditions

Clear-cut difference in the rearrangement of 1-bromo-2-(2-phenyl-3-butenyl)benzene under anionic or radical conditions

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

Reaction mechanisms : Part (i) Radical and radical ion reactions

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