118282-45-4Relevant articles and documents
Stereochimie de l'addition des α-carbanions des nitriles, esters et amides N,N-disubstitues sur la tertio butyl-4 cyclohexanone dans l'ammoniac liquide
Dobrev, Alexandre,Ivanov, Christo,Lattes, Armand,Bon, Maryse
, p. 1084 - 1088 (2007/10/02)
Starting from the hypothesis that the structure of a carbanion influences the stereochemistry of their addition on to carbonyl derivatives, we synthesized various functionalised α carbanions. - For the addition of nitrile anions on 4-t-butyl-cyclohexanone in liquid ammonia, the stereoselectivity depends on the carbeniate structure of the carbanion, but other factors are also operating. - With α,α-disubstituted nitriles the stereoselectivity is surprisingly very high.Cyclic nitriles give different diasteromers depending on the ring strain.Using t-butyl esters we observe a lower stereoselectivity: with α,α-disubstituted esters the diastereomeric ratio is nearly one. - N,N-dibstituted amides have a similar behaviour as in HMPT.With N-phenyl amides yields and stereoselectivities are higher. - In all cases, the axial attack is favored when steric factors are small.When the equatorial attack is predominant, it is possible to correlate this orientation with the predominating enolate structure of the carbanion with a phenyl group in the α position. - A special attention is focussed on N-aryl acetamides where electronic effects can be important, and also on steric effects caused by α-substitution.