65109-01-5Relevant academic research and scientific papers
RADIKALISCHE REAKTIONSWEGE BEI THERMISCH INDUZIERTEN UMSETZUNGEN VON ZIRCONOCENKOMPLEXEN
Erker, G.,Rosenfeldt, F.
, p. 1285 - 1292 (2007/10/02)
The formation of products 2, 3 and 4(a-l) from both the reaction of εta2-bezophenone zirconocene 1 with alkyl halides and the thermolysis of the α-(Cp2ZrCl)-substituted benzhydrylmethylether 9, the latter proceeding with anchimeric assistance of the metal, can be understood assuming a stepwise reaction path through radical intermediates.The proposed intermediate transition-metal benzophenone ketyl 12 exhibits a reaction pattern differing from analogous main-group-metal ketyls.
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.
