20002-32-8Relevant articles and documents
Ashby et al.
, p. 1964 (1975)
NEW METHODOLOGY IN DETERMINING EVIDENCE FOR SINGLE ELECTRON TRANSFER IN THE REACTION OF GRIGNARD REAGENTS WITH KETONES
Zhang, Yunshi,Wenderoth, Bernd,Su, Wei-Yang,Ashby, E. C.
, p. 29 - 38 (1985)
A new method is reported to determine the existence of single electron transfer in the reaction of Grignard reagents with ketones.The method involves the determination of pseudo-first order rate constants by following the rate of disappearance of the paramagnetic intermediate and relating the rate of this disappearance to the appearance of the product.The reactions of methyl-, phenyl- and t-butyl-Grignard reagents with substituted benzophenones were examined.This method should be applicable to a wide range of organometallic reactions.
Organometallic Reaction Mechanisms. 17. Nature of Alkyl Transfer in Reactions of Grignard Reagents with Ketones. Evidence for Radical Intermediates in the Formation of 1,2-Addition Product Involving Tertiary and Primary Grignard Reagents
Ashby, E. C.,Bowers, Joseph R.
, p. 2242 - 2250 (2007/10/02)
When a Grignard reagent reacts with an aromatic ketone, a radical anion-radical cation pair is formed which can collapse to give 1,2-addition product or dissociate to form a radical anion and a free radical within the solvent cage which in turn can collapse to 1,2-addition product or a conjugate addition product or escape the solvent cage to form pinacol.The 1,2-addition products, which form after dissociation of the radical anion-radical cation pair, show free-radical character as indicated by the cyclized 1,2-addition products formed from the reaction of a tertiary Grignard reagent probe with benzophenone in THF and from the reaction of a primary Grignard reagent probe (neooctenyl Grignard reagent) with benzophenone in ether.The 1,6-addition products, which come about after dissociation of the radical anion-radical cation pair, show free-radical character as evidenced by the cyclized 1,6-addition products formed in all of the reactions which involve the tertiary probe Grignard reagent (in all solvents studied) with benzophenone and 2-MBP and also in the reaction of the neooctenyl probe Grignard reagent with 2-MBP.