Chemistry Reference
In-Depth Information
TABLE 7.11. Asymmetric Hydrogenation of
β
- Keto Esters
O
O
OH
O
Chiral catalyst
∗
R
1
XR
2
R
1
XR
2
Reaction
Conditions
% ee
(Confi g.)
R
1
X R
2
Catalyst
S
/
C
Reference
RuCl
2
[(
R
) - BINAP]
Me
OMe
2,000
MeOH, 23 ° C,
100 atm H
2
> 99 (
R
)
18a
RuCl
2
[(
S
) -
7
)](DMF)
n
Me
OMe
1,260
MeOH, 100 ° C,
100 atm H
2
99 (
S
)
239a
RuBr
2
[(
S
) -
NAPhePHOS]
Me
OMe
100
MeOH, 50 ° C,
50 atm H
2
97 (
S
)
241
Ru[(
R
) -
BisbenzodioxanPhos]
Cl
2
(DMF)
n
Me
OMe
1,000
MeOH, 80 ° C,
50 psi H
2
98.1 (
R
)
242,247,
248
RuCl
2
[(
S
) - BIFAP]
(DMF)
n
Me
OMe
1,000
MeOH, 70 ° C,
100 atm H
2
100 (
S
)
243
Ru[(+) - (tetraMe -
BITIANP)]Cl
2
(DMF)
n
Me
OEt
1,000
MeOH, 70 ° C,
100 atm H
2
99 (
R
)
195b
Ru(+) - (tetraMe -
BITIOP)Cl
2
(DMF)
n
Me
OEt
1,000
EtOH, 70 ° C,
100 atm H
2
98 (
S
)
196
Ru[(
S
) - P - Phos)]
Cl
2
(DMF)
n
Me
OMe
400
MeOH/CH
2
Cl
2
,
70 ° C, 50 psi H
2
98.5
132
Ru[(
R
) - C
4
- TunePhos)
Cl
2
(DMF)
n
Me
OMe
100
MeOH, 60 ° C,
750 psi H
2
99.1 (
R
)
23a
Ru[(
S
) - FUPMOP]
(p - cymene)I
2
Me
OMe
1,000
MeOH/CH
2
Cl
2
,
30 - 40 ° C, 30 atm
H
2
100 (
S
)
244
Ru[(
R
) - BIMOP)]
(p - cymene)I
2
Me
OMe
1,000
MeOH/CH
2
Cl
2
,
30 - 40 ° C, 30 atm
H
2
99 (
R
)
245
Me
OMe
100
MeOH, 50 ° C,
20 atm H
2
194
Ru[(
R
) - MeO - BIPHEP)]
Br
2
>
99 (
R
)
Me
OMe
100
MeOH, 80 ° C,
10 atm H
2
194
Ru[(
S
) - BIPHEMP)]Br
2
>
99 (
S
)
Ru[(
R
) - difl uorphos]Br
2
Me
OMe
100
MeOH, 50 ° C,
4 bar H
2
99 (
S
)
206
{Ru[(
R
) - 4,4
-
diamBINAP]Br
2
}
(Br
-
)
2
′
Me
OMe
1,000
H
2
O, 50 ° C, 40 bar
H
2
99 (
S
)
246
Ru[(
S
) -
[2,2] PHANEPHOS]
(CF
3
COO)
2
Me
OMe
250
MeOH/H
2
O,
Bu
4
NI,
96 (
R
)
59b
−
5 ° C,
50 psi H
2
