Catalytic enantioselective addition of organometallic reagents to N-formylimines using monodentate phosphoramidite ligands.
The asymmetric synthesis of protected amines via the copper/phosphoramidite-catalyzed addition of organozinc and organoaluminum reagents to N-acylimines, generated in situ from aromatic and aliphatic alpha-amidosulfones, is reported. High yields of optically active N-formyl-protected amines and enantioselectivities up to 99% were obtained. Under the reaction conditions, partial oxidation of the phosphoramidite ligand to the corresponding phosphoric amide was detected. A preliminary study on the origin and the effect on the catalytic addition reaction is presented.
Pizzuti
Maria Gabriella
MG
Department of Organic and Molecular Inorganic Chemistry, Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747, AG Groningen, The Netherlands.
Minnaard
Adriaan J
AJ
Feringa
Ben L
BL
D002384:Catalysis; D003300:Copper / Q000737:chemistry; D005561:Formates / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D009943:Organophosphorus Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D013451:Sulfonic Acids / Q000737:chemistry; D013452:Sulfonium Compounds / Q000737:chemistry; D014050:Toluene / Q000737:chemistry
D005561:Formates; D007097:Imines; D008024:Ligands; D009942:Organometallic Compounds; D009943:Organophosphorus Compounds; D013451:Sulfonic Acids; D013452:Sulfonium Compounds; C434331:phosphoramidite; C030544:formic acid; D014050:Toluene; D003300:Copper; C005741:sulfamic acid