Page 24 - Demo-1

Shvo's Catalyst - Mechanism of Action OO Ph
Ph
Ph O
Ph Ph H Ph Ph Ph OH
Ph Ph Ru H Ru Ph Ph Ph Ph + Ph Ph
OCCO Ru Ru
OC CO OC H Shvo's Catalyst OC
OC OC
Ph Ph Ph
Ph O Ph OH Ph O
Ph Ph + OH Ph Ph O Ph Ph H*+ +R'
OH
Ru RR' Ru RR' Ru RH*
OC OC H* OC OC OC OC
Pamies, O.; Backvall, J.-E. Chem. Rev. 2003, 103, 3247
Combination Enzyme-Metal Catalysis - DKR of Alcohols/Diols
OH
R2
OAc
80%, 98% ee
CALB p-Cl-C6H4-OAc (3 equiv)
Shvo's Ru Cat. (2 mol%) PhCH3
OAc
R1 R2
78-92% yield 91- >99% ee
OAc
65%, >99% ee
OH
OH meso-product
OAc
80%, >99% ee
OH
OAc OAc
OAc OAc
OAc
77%, >99% ee
OAc OAc
OAc
5
90%, >97% ee
R1
O
88%, >99% ee
79%, >99% ee
CALB p-Cl-C6H4-OAc (3 equiv)
Shvo's Ru Cat. (4 mol%) PhCH3
63%, >99% ee
OH
OH
OH (R,R)-product
86
43%, >99% ee AcO
(74:26)
OAc
OAc 78%, >99% ee
(100:0)
+
OAc Bn N
90%, >99% ee OAc (R,R:meso)
(38:62)
63%, >97% ee OAc (90:10)
N
: OAc
OAc
14
77%, >99% ee (98:2)
64%, >96% ee (89:11)
Pamies, O.; Backvall, J.-E. Chem. Rev. 2003, 103, 3247