S. Matsunaga et al., Catalytic enantioselective meso-epoxide ring opening reaction with phenolic oxygen nucleophile promoted by gallium heterobimetallic multifunctional complexes, J AM CHEM S, 122(10), 2000, pp. 2252-2260
The catalytic enantioselective meso-epoxide ring opening reaction with phen
olic oxygen nucleophile (4-methoxyphenol) is described for the first time h
erein. This reaction was first found to he promoted by (R)-GaLB (Ga = galli
um, L = lithium, B = (R)-BINOL), giving a variety of epoxide opening produc
ts in good to high ee (67-93% ee). However, chemical yield was only modest
(yield 31-75%). despite the use of more than 20 mol % GaLB. This was due to
the undesired ligand exchange between BINOL and 4-methoxyphenol, which res
ulted in the decomplexation of GaLB. Application of various known chiral li
gands such as 6,6'-bis((triethylsilyl)ethynyl)-BINOL and H-8-BINOL were exa
mined, but satisfactory results were not obtained. To overcome this problem
a novel linked-BINOL containing coordinative oxygen atom in the linker has
been developed. By linking two BINOL units in GaLB, the stability of the G
a-complex was greatly improved. Using 3-10 mol % (R,R)-Ga-Li-linked-BINOL c
omplex, a variety of epoxide opening reactions were found to proceed smooth
ly, affording products in analogous ee (66-96% ee) and in much higher yield
(yield 67-94%) compared to (R)-GaLB. The structure of the LiCl free Ga-Li-
linked-BINOL complex was elucidated by X-ray analysis. This is the first X-
ray data for an asymmetric catalyst containing gallium. The possible mechan
ism of the entitled reaction is also discussed, based on the X-ray structur
e of the Ga-complex.