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Ruthenium-Catalyzed Hydrogenations (Cont'd)
OO H2 OHO OOH
P(OCH ) [(S)-BINAP]Ru(II) 32 MeOH
P(OCH3)2
Br
P
H3C
H O HOH
fosfomycin
Br
80% de, 98% ee
Ts Ph N
O Ru OH
Ph Ph NTs Cl Ph
Ph
OMe
H2, HCO2H, Et3N Ph
O OH
O O
N
Ru(S-C3-Tunephos) MeOH, 50oC
100 bar
OH O
N
OMe
100%, 97% de, >99% ee
O PPh2
n
O PPh2
(S)-Tunephos
>99% ee, anti:syn >97:3
Noyori, R.; Tokunaga, M.; Kitamura, M. Bull. Chem. Soc. Jpn. 1995 68, 36 Lei, A.; Wu, S.; He, M.; Zhang, X. J. Am. Chem. Soc. 2004 126, 1626
DKR via Cross-Coupling
MgCl RH
Ph
LL Ph
Br cat. NiCl2 / L*
Ph
>95%, >80% ee
L*=MeN PPh 2 2
(R = iPr, sBu, tBu)
MgBrCl
LL
Ph CH3 H
Br
Ph
MgCl
H CH3
Ph
MgCl
CH3 H
MgBrCl
Ni
H CH3
(L2)(Br)Ni
H CH3
Ni
Br
Ph
Ph
CH3 H
Ward, R. S. Tetrahedron: Asymmetry 1995, 6, 1475
