27608-01-1Relevant academic research and scientific papers
Making mixtures to solve structures: structural elucidation via combinatorial synthesis
Lengkeek, Nigel A.,Greenwood, Paul F.,Nguyen, Blake,Koutsantonis, George A.,Piggott, Matthew J.
experimental part, p. 141 - 150 (2010/10/19)
A domino Horner-Wadsworth-Emmons olefination strategy has been used to prepare homologous series of (polyen)ones, and through combinatorial elaboration, corresponding families of highly branched hydrocarbons. Gas chromatography-mass spectrometry of the mixtures has enabled the rapid and unambiguous identification of several highly branched alkanes of geochemical importance. This is the first example of the use of combinatorial synthesis for the elucidation of structural connectivity.
On the mechanism of the copper-catalyzed enantioselective 1,4-addition of Grignard reagents to α,β-unsaturated carbonyl compounds
Harutyunyan, Syuzanna R.,Lopez, Fernando,Browne, Wesley R.,Correa, Arkaitz,Pena, Diego,Badorrey, Ramon,Meetsma, Auke,Minnaard, Adriaan J.,Feringa, Ben L.
, p. 9103 - 9118 (2007/10/03)
The mechanism of the enantioselective 1,4-addition of Grignard reagents to α,β-unsaturated carbonyl compounds promoted by copper complexes of chiral ferrocenyl diphosphines is explored through kinetic, spectroscopic, and electrochemical analysis. On the basis of these studies, a structure of the active catalyst is proposed. The roles of the solvent, copper halide, and the Grignard reagent have been examined. Kinetic studies support a reductive elimination as the rate-limiting step in which the chiral catalyst, the substrate, and the Grignard reagent are involved. The thermodynamic activation parameters were determined from the temperature dependence of the reaction rate. The putative active species and the catalytic cycle of the reaction are discussed.
Synthese de cetones a partir de N-phenyl imidothioesters et par l'intermediaire de cetenimines
El-Jazouli, Mustapha,Lage, Nadia,Masson, Serge,Thuillier, Andre
, p. 883 - 888 (2007/10/02)
The thermal decomposition of metallated N-phenyl imidothioesters (lithium or magnesium alkylthio-enaminates generated by either deprotonation or 1,4-addition) led to ketenimines which were trapped in situ by organo-lithium or magnesium compounds to give metallated imines, readily hydrolysed into ketones.This sequence allowed the use of imidothioesters as acyl cation equivalents and also successive and regioselective > 1,3-additions of two different organometallics to an α-unsaturated imidothioester.Ar-turmerone, 2,6-dimethyl-2,7-octadien-4-one, iso-artemisia ketone, α-atlantone and other unsymmetrical ketones were synthesized by this procedure.
A New Route to Unsymmetrical Ketones from Thioimidates via Ketenimines; a One-pot Synthesis of ar-Turmerone
Jazouli, Mustapha El,Masson, Serge,Thuillier, Andre
, p. 1598 - 1599 (2007/10/02)
Ketones may be synthesised by the generation and thermal decomposition of thio-N-metallated-enamines followed by trapping of the resulting ketenimines with an organometallic reagent.
Conjugate Addition Reactions of α,β-Unsaturated Ketones with Higher Order, Mixed Organocuprate Reagents, R2Cu(CN)Li2
Lipshutz, Bruce H.,Wilhelm, Robert S.,Kozlowski, Joseph A.
, p. 3938 - 3942 (2007/10/02)
Conjugate reactions of mixed cuprates R2Cu(CN)Li2 with α,β-unsaturated ketones are reported.These reagents, in most cases, react extremely rapidly affording the corresponding alkylated ketones in high yields.Attempts at trapping the intermediate enolates appeared to be successful using MeI as electrophile; however, the method is not general and was, therefore, not pursued.The effects of solvent and ligand composition on R2Cu(CN)Li2 as well as on the more highly mixed species RTRRCu(CN)Li2 have been examined.The selectivity of ligand transfer in these latter,second generation organocuprates is also discussed.
CHEMISTRY OF HIGHER ORDER, MIXED ORGANOCUPRATES. 3. REACTIONS OF α,β-UNSATURATED KETONES.
Lipshutz, Bruce H.,Wilhelm, Robert S.,Kozlowski, Joseph
, p. 3755 - 3758 (2007/10/02)
Organocuprates of general formula R2Cu(CN)Li2 react rapidly with α,β-unsaturated ketones at low temperatures and in high yields to deliver ligands in a conjugate manner.These reagents apparently do not require the use of additives for stabilizing or solubilizing purposes.
