Insight into substrate binding in Shibasaki's Li3(THF)n(BINOLate)3Ln complexes and implications in catalysis.
Heterobimetallic Lewis acids M 3(THF) n (BINOLate) 3Ln [M = Li, Na, K; Ln = lanthanide(III)] are exceptionally useful asymmetric catalysts that exhibit high levels of enantioselectivity across a wide range of reactions. Despite their prominence, important questions remain regarding the nature of the catalyst-substrate interactions and, therefore, the mechanism of catalyst operation. Reported herein are the isolation and structural characterization of 7- and 8-coordinate heterobimetallic complexes Li 3(THF) 4(BINOLate) 3Ln(THF) [Ln = La, Pr, and Eu], Li 3(py) 5(BINOLate) 3Ln(py) [Ln = Eu and Yb], and Li 3(py) 5(BINOLate) 3La(py) 2 [py = pyridine]. Solution binding studies of cyclohexenone, DMF, and pyridine with Li 3(THF) n (BINOLate) 3Ln [Ln = Eu, Pr, and Yb] and Li 3(DMEDA) 3(BINOLate) 3Ln [Ln = La and Eu; DMEDA = N, N'-dimethylethylene diamine] demonstrate binding of these Lewis basic substrate analogues to the lanthanide center. The paramagnetic europium, ytterbium, and praseodymium complexes Li 3(THF) n (BINOLate) 3Ln induce relatively large lanthanide-induced shifts on substrate analogues that ranged from 0.5 to 4.3 ppm in the (1)H NMR spectrum. X-ray structure analysis and NMR studies of Li 3(DMEDA) 3(BINOLate) 3Ln [Ln = Lu, Eu, La, and the transition metal analogue Y] reveal selective binding of DMEDA to the lithium centers. Upon coordination of DMEDA, six new stereogenic nitrogen centers are formed with perfect diastereoselectivity in the solid state, and only a single diastereomer is observed in solution. The lithium-bound DMEDA ligands are not displaced by cyclohexenone, DMF, or THF on the NMR time scale. Use of the DMEDA adduct Li 3(DMEDA) 3(BINOLate) 3La in three catalytic asymmetric reactions led to enantioselectivities similar to those obtained with Shibasaki's Li 3(THF) n (BINOLate) 3La complex. Also reported is a unique dimeric [Li 6(en) 7(BINOLate) 6Eu 2][mu-eta (1),eta (1)-en] structure [en = ethylenediamine]. On the basis of these studies, it is hypothesized that the lanthanide in Shibasaki's Li 3(THF) n (BINOLate) 3Ln complexes cannot bind bidentate substrates in a chelating fashion. A hypothesis is also presented to explain why the lanthanide catalyst, Li 3(THF) n (BINOLate) 3La, is often the most enantioselective of the Li 3(THF) n (BINOLate) 3Ln derivatives.
Wooten
Alfred J
AJ
P. Roy and Diana T. Vagelos Laboratories, Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, USA.
Carroll
Patrick J
PJ
Walsh
Patrick J
PJ
D001667:Binding, Competitive; D002384:Catalysis; D005029:Ethylenediamines / Q000737:chemistry; D005663:Furans / Q000737:chemistry*; D028581:Lanthanoid Series Elements / Q000737:chemistry*; D018020:Lithium Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008672:Metals, Alkali / Q000737:chemistry*; D009284:Naphthols / Q000737:chemistry; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D012996:Solutions
C406944:BINOL, naphthol; D005029:Ethylenediamines; D005663:Furans; D028581:Lanthanoid Series Elements; D018020:Lithium Compounds; D008672:Metals, Alkali; D009284:Naphthols; D009942:Organometallic Compounds; D012996:Solutions; C018674:tetrahydrofuran