Chemistry Reference
In-Depth Information
TABLE 7.5. Asymmetric Hydrogenation of
α
- (Acyloxyl) Acrylates
R
2
R
2
Rh or Ru catalyst
H
2
R
1
R
1
*
OA c
OAc
% ee
(Confi g.)
Catalyst
R
1
R
2
E
/
Z
Reaction Conditions
a
Reference
(
R,R
) - Et - DuPhos -
Rh
H
CO
2
Et
N/A
MeOH, rt, 2 atm H
2
>
99 (
R
)
164,165
H
CO
2
Me
N/A
Acetone, rt, 1 atm H
2
81c
(
R
) - (
S
) -
87
- Rh
94.9 (
S
)
H
CO
2
Me
N/A
MeOH, rt, 1 atm H
2
168
(
R
) - (
S
) -
93
- Rh
98 (
S
)
i
Pr
CO
2
Et
MeOH, rt, 3 atm H
2
170
(
R,R
) - DIPAMP - Rh
E
/
Z
92 (
S
)
i
Pr
CO
2
Et
MeOH, rt, 6 atm H
2
166
(
R,R
) - Et - DuPhos -
Rh
E
/
Z
96.1 (
R
)
i
Pr
(
R
) - BINAP - Ru
CO
2
Et
E
/
Z
MeOH, 50 ° C, 50 atm
H
2
98 (
S
)
170
Ph
CO
2
Et
MeOH, rt, 3 atm H
2
170
(
R,R
) - DIPAMP - Rh
Z
88 (
S
)
Ph
CO
2
Et
MeOH, rt, 3 atm H
2
166
(
R,R
) - Et - DuPhos -
Rh
E
/
Z
95.6 (
R
)
H
Ph
N/A
MeOH, rt, 3 atm H
2
164
(
S,S
) - Me - DuPhos -
Rh
89 (
S
)
(
S,S,R,R
) -
TangPhos - Rh
H
Ph
N/A
EtOAc, rt, 20 psi H
2
96 (
R
)
169
(
R,R,S,S
) -
DuanPhos - Rh
H
Ph
N/A
THF, rt, 20 psi H
2
97 (
R
)
5 8
(
R,R,S,S
) -
DuanPhos - Rh
H
2 - Np
N/A
THF, rt, 20 psi H
2
98 (
R
)
5 8
(
S,S
) - Me -
DuPhos - Rh
H
1 - Np
N/A
MeOH, rt, 3 atm H
2
93 (
S
)
164
Et -
35
- Rh
H
1 - Np
N/A
MeOH, rt, 3 atm H
2
95 (
S
)
68b
(
S,S,R,R
) -
TangPhos - Rh
H
1 - Np
N/A
EtOAc, rt, 20 psi H
2
97 (
R
)
169
(
S
) - C2 -
TunePhos - Ru
H
1 - Np
N/A
EtOH/CH
2
Cl
2
, rt,
3 atm H
2
97.7 (
S
)
171
12
- Rh
H
1 - Np
N/A
EtOH/CH
2
Cl
2
, rt,
50 psi H
2
96.7 (
R
)
134
12
- Rh
H
p
- FC
6
H
4
N/A
EtOH/CH
2
Cl
2
, rt,
50 psi H
2
97.1 (
R
)
134
(
R,R
) - Me - DuPhos -
Rh
H
PhCH = CH (
E
)
N/A
THF, rt, 2 atm H
2
94 (
R
)
167
(
R,R
) - Et - BPE - Rh
H
CF
3
N/A
MeOH, rt, 2 atm H
2
>
95 (
R
)
164
a
Complete conversion unless otherwise noted.
