The benzyne aza-Claisen reaction.
Adding an aryne to a tertiary allylamine affords o-allylaniline products of an aza-Claisen rearrangement. The aryne simultaneously provides the pi component for the rearrangement and the quaternization event that lowers the activation energy for the sigmatropic shift. The reaction was applied to the synthesis of medium-ring benzannulated amines (see scheme).
Cant
Alastair A
AA
School of Chemistry, University of Edinburgh, King's Buildings, West Mains Road, Edinburgh, EH9 3JJ, UK.
Bertrand
Guillaume H V
GH
Henderson
Jaclyn L
JL
Roberts
Lee
L
Greaney
Michael F
MF
D000588:Amines / Q000737:chemistry; D001372:Aza Compounds / Q000737:chemistry*; D001555:Benzene Derivatives / Q000737:chemistry*; D002384:Catalysis; D010880:Piperidines / Q000138:chemical synthesis / Q000737:chemistry
D000588:Amines; D001372:Aza Compounds; D001555:Benzene Derivatives; D010880:Piperidines; C524146:benzyne