6052-56-8Relevant academic research and scientific papers
Heteropolyacid-catalyzed direct deoxygenation of propargyl and allyl alcohols
Egi, Masahiro,Kawai, Takuya,Umemura, Megumi,Akai, Shuji
experimental part, p. 7092 - 7097 (2012/10/07)
The combination of H3[PW12O40] ?nH2O (1 mol %) and Et3SiH led to the direct catalytic deoxygenation of propargyl alcohols, in which proper solvent selection Cl(CH2)2Cl vs CF3CH2OH was the key to obtaining better product yields. Under similar conditions, the deoxygenation of allyl alcohols proceeded to give thermodynamically stable alkenes with migration of the double bonds in good yields.
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.
