Iminoesters, reactions with amines

The reaction of aliphatic primary amines with alkyl a-hydrogenoperfluorocar-boxylates leads to the corresponding P-alkyl iminoesters as the major or the sole tautomers, depending on the length of the perfluoroalkyl chain [ 103] (equation 89). 

An enantioselective version of this reaction has been reported by Rueping et al.102 Treatment of an a-iminoester and an alkyne with silver acetate and a binol phosphate derivative gave propargylic amines with the highest enantiomeric ratio (er) reported as 96 4. Although the proposed catalytic cycle invoked the in situ formation of the... 

Compounds (82)-(84) were synthesized as outlined in Scheme 3.12. Reaction of naltrexone with 4-hydrazinobenzonitrile [143] under Fischer indole conditions afforded the 5 -nitrile (86) which was catalytically hydrogenated to the primary amine (87) using Raney nickel. The amidines (82)-(84) were prepared by reacting amine (87) with the appropriate iminoester [144, 145],... 

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