23 Asymmetric Catalysis and Chromatographic …
491
Table 23.12 Enantioselective Friedel–Crafts reactions of dialkylanilines with β-nitrostyrene
catalyzed by (R)-MOF-12
OH
OH
HO 2 C
HO 2 C
(R)12
Cu(NO 3 ) 2
(R)-MOF-12
60
NO 2
NO 2
N
R 1
R 1
N
R 1
R 1
R 2
R 2
+
(R)-MOF-12
Entry
R 1
R 2
Solv.
Time (h)
Yield (%)
Ee (%)
1
Me
H
EtOH
48
95
98 (R)
2
Et
H
2-PrOH
72
91
95
3
n-Pr
H
2-PrOH
72
46
84
4
C H 2 Ph
H
EtOH
72
5
26
5
Me
Me
EtOH
48
93
97
6
Me
Cl
EtOH
72
56
98
7
Me
OMe
2-PrOH
48
96
94
8
-(CH 2 ) 5 -
EtOH
72
62
99
Table 23.13 Enantio- and diastereoselective Friedel–Crafts reactions of pyrroles with βnitrostyrene catalyzed by (R)-MOF-12
N
R
+
(R)-MOF-12
NO 2
N
R
O 2 N
NO 2
+
60
24 h
N
R
NO 2
1:1 adduct
1:2 adduct
Entry
R
Solv.
1:1 adduct
1:2 adduct
Yield (%)
Ee (%)
Yield(%)
Ee(%)
Dr
1
H
2-PrOH
44
75
21
93
69:31
2
Me
EtOH
44
80
15
97
81:19