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Scheme 4. Synthesis of Seven-and Eight-Membered Fluorinated Cyclic β-Amino Alcohol Derivatives Scheme 5. Synthesis of Fluorinated Amino Macrolactones 17 Scheme 6. Addition of Ester Lithium Enolates of 4-Pentenoic Acid to Imidoyl Chlorides Scheme 7. Imine Reduction−RCM versus RCM−Imine Metathesis Strategies Chemical Reviews Review dx.

N-Sulfinyl amines have been successfully employed as nitrogen nucleophiles for the asymmetric intramolecular aza-Michael reaction. The synthetic strategy involves a cross-metathesis reaction followed by the Michael-type cyclization, either in a base-catalyzed two-step procedure or in a tandem fashion. The developed methodology allows access to chiral substituted pyrrolidines and piperidines bearing one or two stereocenters and it has been applied to the synthesis of the piperidine alkaloid (-)-pinidinol.

A highly stereoselective synthesis of fluorinated 1,3-disubstituted isoindolines is described. To this end, a tandem reaction consisting of a diastereoselective addition of fluorinated nucleophiles to Ellman's N-(tert-butanesulfinyl)imines followed by an intramolecular aza-Michael reaction has been developed. This strategy allows for the construction of isoindolines bearing several degrees of fluorination (mono-, di-, or trifluoromethyl as well as heavier fluorinated groups). In the majority of all cases, the products are formed as single isomers.