Structures and Reactivities of Sodiated Evans Enolates: Role of Solvation and Mixed Aggregation on the Stereochemistry and Mechanism of Alkylations

Oxazolidinone-based sodiated enolates (Evans enolates) were generated using sodium diisopropylamide (NaDA) or sodium hexamethyldisilazide (NaHMDS) in the presence of N,N,N',N'-tetramethylethylenediamine (TMEDA), ( R,R)- trans- N,N,N',N'-tetramethylcyclohexanediamine [( R,R)-TMCDA], or ( S,S)-TMCDA. ¹³C NMR spectroscopic analysis in conjunction with the method of continuous variations (MCV), x-ray crystallography, and density functional theory (DFT) computations revealed the enolates to be octahedral bis-diamine-chelated monomers. Rate and computational studies of an alkylation with allyl bromide implicate a bis-diamine-chelated-monomer-based transition structure. The sodiated Evans enolates form mixed dimers with NaHMDS, NaDA, or sodium 2,6-di- tert-butylphenolate, the reactivities of which are examined. Stereoselective quaternizations, aldol additions, and azaaldol additions are described.