69035-58-1Relevant academic research and scientific papers
Beryllium dichloride: Efficient promoter for the addition of organolithiums and organomagnesiums to cyclohexen-2-one
Krief, Alain,De Vos, Marie Joelle,De Lombart, Stephane,Bosret, Jean,Couty, Francois
, p. 6295 - 6298 (1997)
Organoberyllium compounds, generated by transmetallation from Grignard and organolithium reagents react with 2-cyclohexenone to give predominantly the adducts resulting from conjugated addition. The chemoselectivity of this reaction was found to be highly dependent upon the nature of organic moiety and of the conditions used.
Palladium-catalyzed oxidative rearrangement of tertiary allylic alcohols to enones with oxygen in aqueous solvent
Li, Jingjie,Tan, Ceheng,Gong, Jianxian,Yang, Zhen
supporting information, p. 5370 - 5373 (2015/01/09)
A one-pot procedure for Pd(TFA)2-catalyzed 1,3-isomerization of tertiary allylic alcohols to secondary allylic alcohols followed by a Pd(TFA)2/neocuproine-catalyzed oxidative reaction to β-disubstituted-α,β-unsaturated kenones was developed. (Chemical Equation Presented).
Highly regioselective control of 1,2-addition of organolithiums to α,β-unsaturated compounds promoted by lithium bromide in 2-methyltetrahydrofuran: A facile and eco-friendly access to allylic alcohols and amines
Pace, Vittorio,Castoldi, Laura,Hoyos, Pilar,Sinisterra, José Vicente,Pregnolato, Massimo,Sánchez-Montero, Ma. José
supporting information; experimental part, p. 2670 - 2675 (2011/04/23)
Very high regioselective 1,2-addition of organolithiums to α,α-unsaturated carbonyl-like compounds (ketones, aldehydes, and imines) in the presence of LiBr was achieved by carrying out reactions in the sustainable solvent 2-methyltetrahydrofuran. Excellent yields (in isolated product) of allylic alcohols and allylic amines were recovered under a simple experimental procedure at 0 °C.
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.
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 (2007/10/02)
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.
REACTIVITY OF α,β-UNSATURATED ACETALS AND KETALS TOWARD ORGANOLITHIUM REAGENTS IN PENTANE
Mioskowski, Charles,Manna, S.,Falck, J. R.
, p. 519 - 522 (2007/10/02)
Depending upon structure and reaction conditions, α,β-unsaturated acetals and ketals react with organolithium reagents in pentane by addition, substitution, or proton abstraction.
SYN REGIOSELECTIVITY OF THE HYDROPEROXIDATION OF CYCLO-ALKENES WITH SINGLET OXYGEN
Jefford, Charles W.,Rimbault, Christian G.
, p. 91 - 94 (2007/10/02)
The regioselectivity of hydroperoxidation of 1-alkylcycloalkenes is rationalized in terms of the formation of a zwitterionic peroxide.
