Chemistry Reference
In-Depth Information
TABLE 8B.50. Asymmetric Rh - Catalyzed Allylations of Boronic Acids and Organozinc
Reagents according to Gong et al.
NO
2
NO
2
ArM
Rh complex,
(
R
)- or (
S
)-
BINAP
,
react. cond.
OAc
Ar
Entry
ArM
Rh Complex
React. Cond.
Yield (%)
ee (%)
1
PhB(OH)
2
Rh(acac)(C
2
H
4
)
2
Dioxane/H
2
O, 50 ° C, 20 h
41
94
2
PhB(OH)
2
[Rh(OH)(COD)]
2
Dioxane/H
2
O, 50 ° C, 20 h
56
97
3
4 - F - C
4
H
4
B(OH)
2
[Rh(OH)(COD)]
2
Dioxane/H
2
O, 50 ° C, 20 h
61
98
4
4 - Cl - C
4
H
4
B(OH)
2
[Rh(OH)(COD)]
2
Dioxane/H
2
O, 50 ° C, 20 h
64
99
5
3 - MeO - C
4
H
4
B(OH)
2
[Rh(OH)(COD)]
2
Dioxane/H
2
O, 50 ° C, 20 h
58
96
6
PhZnCl
Rh(acac)(C
2
H
4
)
2
THF, 0 ° C, 25 h
93
93
7
4 - MeO - C
4
H
4
ZnCl
Rh(acac)(C
2
H
4
)
2
THF, 0 ° C, 25 h
79
89
8
4 - F - C
4
H
4
ZnCl
Rh(acac)(C
2
H
4
)
2
THF, 0 ° C, 25 h
91
96
TABLE 8B.51. Enantioselective Ring Opening of Oxabicycles
OH
O
RB(OH)
2
[Rh(COD)Cl]
2
/
(
R
,
pS
)-
L40b
, THF,
aq. Cs
2
CO
3
, rt, 15 h
OR'
R
OR'
OR'
OR'
Entry
R
′
R
Yield (%)
ee (%)
1
Me
Ph
91
95
2
Me
4 - Cl - C
6
H
4
95
95
3
Me
4 - MeO - C
6
H
4
87
96
4
Me
3 - Cl - C
6
H
4
73
99
5
Pmb
1 - Hexenyl
95
92
OMe
Cl
N
PPh
2
PPh
2
P(
t
Bu)
2
PPh
2
PPh
2
PXyl
2
PXyl
2
MeO
MeO
MeO
Fe
PPh
2
MeO
N
Cl
OMe
(
S
)-
BINAP
(
L23a
)
(
R
,
pS
)-
L40b
L56
L57
Figure 8B.32.
Ligands used in asymmetric Rh-catalyzed allylations of hard nucleophiles.
