Pyridylalanine (pal)-peptide catalyzed enantioselective allenoate additions to N-acyl imines.
An amine-catalyzed reaction has been discovered that couples alpha-allenic esters with N-acyl imines in good to excellent yields (up to 88%). Extension of this methodology from the study of achiral pyridine-based catalysis to chiral peptide-based scaffolds is presented. The approach culminated in the identification of a tetrameric peptide sequence containing an embedded pyridylalanine (Pal) residue as an efficient asymmetric catalyst for enantioselective coupling reactions. The unique allenic products are obtained with enantiomer ratios of up to approximately 95:5 (up to >98:2 following recrystallization).
Department of Chemistry, Yale University, P.O. Box 208107, New Haven, Connecticut 06520-8107, USA.
Bryan J
BJ
Cowen
Lindsey B
LB
Saunders
Scott J
SJ
Miller
D000409:Alanine / Q000737:chemistry*; D002384:Catalysis; D007097:Imines / Q000138:chemical synthesis / Q000737:chemistry*; D008968:Molecular Conformation; D009281:Naphthalenes / Q000737:chemistry*; D010455:Peptides / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*; D013237:Stereoisomerism
D007097:Imines; D009281:Naphthalenes; D010455:Peptides; D011725:Pyridines; C110055:allenolic acid; D000409:Alanine