208582-21-2Relevant articles and documents
A direct conversion of α,β-unsaturated ketones to vinylcyclopropanes: New zirconium-mediated reaction
Bertus, Philippe,Gandon, Vincent,Szymoniak, Jan
, p. 171 - 172 (2000)
Various vinylcyclopropanes are synthesized from α,β-unsaturated ketones via a zirconium-mediated [1,2]-addition-deoxygenative cyclopropanation sequence; the latter step surprisingly proceeds under specific protic conditions.
Effect of InCl3 on the addition of Grignard reagents to α,β-unsaturated carbonyl compounds
Kelly, Brian G.,Gilheany, Declan G.
, p. 887 - 890 (2007/10/03)
Control of 1,2- versus 1,4-addition of organometallic reagents to enones remains a long-standing problem. There is still no satisfactory 1,2-directing agent comparable to the 1,4-directing effect of copper salts. We report that the presence of just 5 mol% indium(III) chloride can significantly alter the amount of 1,2-product formed in these reactions.
Mechanism of the Grignard Adddition Reaction. XVI. Homolytic and Concerted Mechanisms in the Reaction of α,β-Unsatureted Carbonyl Compounds with Grignard Reagents
Holm, Torkil
, p. 925 - 929 (2007/10/02)
Kinetic measurements have shown that the addition of Grignard reagents to α,β-unsaturated carbonyl compounds takes place either by a concerted mechanism or by a homolytic mechanism.Phenylmagnesium bromide, which is incapable of homolysis, reacts rapidly in a 1,4-fashion if an s-cis conformation exists between the C=C and the C=O bonds, but only 1,2-addition takes place if the conformation is s-trans.tert-Butylmagnesium bromide is unsuited to the concerted reaction, but 1,4-addition takes place via homolysis.Primary and secondary Grignard reagents, like phenyl, react rapidly in a concerted manner with s-cis substrates, but unlike phenyl, these Grignard reagents may, with s-trans substrates, produce some 1,4-adduct via the homolytic mechanism.
