Asymmetric catalysis via dynamic substrate/ligand/rare earth metal conglomerate.
A highly enantio- and diastereoselective catalytic asymmetric Mannich-type reaction of alpha-cyanoketones and N-Boc imines promoted by an amide ligand/Sc(OiPr)3 catalyst is described. The similar reaction outcome is obtained with/without precomplexation of catalyst, suggesting that reaction components in a non-ordered conglomerate mixture orchestrate to form an ordered transition state during the reaction. Spectroscopic data and Eyring plot are consistent with this assumption.
Nojiri
Akihiro
A
Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, 113-0033 Tokyo, Japan.
Kumagai
Naoya
N
Shibasaki
Masakatsu
M
D000577:Amides / Q000737:chemistry*; D002384:Catalysis; D007097:Imines / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008674:Metals, Rare Earth / Q000737:chemistry*; D008956:Models, Chemical; D009942:Organometallic Compounds / Q000138:chemical synthesis*; D013237:Stereoisomerism
D000577:Amides; D007097:Imines; D007659:Ketones; D008024:Ligands; D008674:Metals, Rare Earth; D009942:Organometallic Compounds