Lanthanide complexes coordinated by N-substituted (R)-1,1'-binaphthyl-2,2'-diamido ligands in the catalysis of enantioselective intramolecular hydroamination.
A new family of lanthanide ionic complexes derived from chiral, substituted (R)-binaphthylamine ligands, [Li(thf)(4)][Ln{(R)-C(20)H(12)(NR)(2)}(2)] (Ln=Yb, Sm, Nd, or Lu), has been synthesized and characterized by X-ray crystal structure analyses. All complexes have been tested as new catalysts for the hydroamination/cyclization of 1-(aminomethyl)-1-allylcyclohexane. Ytterbium complexes proved to be both the most active and the most enantioselective, and the use of the complex [Li(thf)(4)][Yb{(R)-C(20)H(12)(NC(3)H(7))(2)}(2)], bearing isopropyl radicals on the nitrogen atoms, allowed the formation of the corresponding spiropyrrolidine in high yield with up to 70 % ee.
Collin
Jacqueline
J
Laboratoire de Catalyse Moléculaire, ICMMO, Université Paris-Sud, 91405 Orsay, France.
Daran
Jean-Claude
JC
Jacquet
Olivier
O
Schulz
Emmanuelle
E
Trifonov
Alexander
A
D000577:Amides / Q000138:chemical synthesis* / Q000737:chemistry; D000586:Amination; D002384:Catalysis; D018360:Crystallography, X-Ray; D003500:Cyclization; D003510:Cyclohexanes / Q000737:chemistry; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D015394:Molecular Structure; D009281:Naphthalenes / Q000138:chemical synthesis* / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis* / Q000737:chemistry; D013237:Stereoisomerism
D000577:Amides; D003510:Cyclohexanes; D028581:Lanthanoid Series Elements; D009281:Naphthalenes; D009942:Organometallic Compounds