N‐Allylideneamines Derived from Acrolein: Synthesis and Use as Acceptors of Two Nucleophiles

Two practical methods have been developed for the preparation of N‐allylideneamines 1b,c. One involves the isomerization of propargylamines and the other the dehydration of acrolein. N‐Allylideneamines 1b,c thus prepared were used as efficient substrates for 1,4‐ and 1,2‐double nucleophilic addition reactions. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009) N‐Allylideneamines have been synthesized from acrolein and bulky primary amines in the presence of Ti(OEt)4. 1,4‐ and 1,2‐Double nucleophilic addition of ketene silyl (thio)acetals and trimethylsilyl cyanide to N‐allylideneamines gave amino acids and/or valerolactams.