65995-75-7Relevant academic research and scientific papers
METALLORGANISCHE VERBINDUNGEN DER LANTHANOIDE XXXV. BIS(TETRAMETHYLETHYLENDIAMIN)LITHIUM TETRAKIS-t-BUTYLLUTETAT(III):SYNTHESE, MOLEKUELSTRUKTUR UND REAKTIVES VERHALTEN GEGENUEBER α,β-UNGESAETTIGTEN CARBONYLVERBINDUNGEN
Schumann, Herbert,Genthe, Wolfgang,Hahn, Ekkehardt,Pickardt, Joachim,Schwarz, Helmut,Eckart, Klaus
, p. 215 - 226 (1986)
LuCl3 reacts with t-butyllithium in the presence of ether and tetramethylethylene diamine (tmed) to form , the structure of which has been elucidated through complete X-ray analysis.The crystals are orthorhombic with a 20.995(9), b 18.310(7), c 9.527(2) Angstroem, space group P21ab, Z = 4, D(calcd) 1.17 g cm-3, R = 0.035, and 2471 observed reflections.The compound undergoes 1,2-addition to cinnamic aldehyde, benzalacetone, 1-phenylbutene-2-methyl-3-one, 2-methylbutene-3-one and cyclohexanone, respectively, to give after hydrolysis of the reaction mixture α-t-butyl-substituted enoles.The reaction products were identified by means of GC/MS methods.
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.
