8 Earth-Abundant d-Block Metal Nanocatalysis for Coupling …
267
R
1 = Ph, 4-CH 3 -C 6 H 4 , 4-COOCH 3 -C 6 H 4 , C 5 H 11 , 4-F-C 6 H 4
R
2 = Ph, 4-CH 3 -C 6 H 4 , 4-Br-C 6 H 4 , 4-CF 3 -C 6 H 4 , Cy
amine =
+
R
1
R
2
O
+ amine
HNEt 2
HNMeBn
HN
O
HN
[CuA NPs] (2 mol%)
glycerol
100 °C, 12 h
R
2
N
R
1
12 products A
3
Isolated yield: 74-90%
+
R
1
R
1 = Ph, 4-CH 3 -C 6 H 4 , 4-COOCH 3 -C 6 H 4 , C 5 H 11
R
1 = H, 4-Br, 3-CH 3
n = 0, 1
R
2
N
n
CH 3
CH 3
[CuA NPs] (1 mol%)
2 equiv. TBHP
glycerol
100 °C, 2 h
N
H 3 C
n
7 products
Isolated yield: 72-91%
R
2
X
+ amine
N
[CuA NPs] (2.5 mol%)
glycerol
100 °C, 12 h
R
1
R
1
R
2
R
3
Cl
9
N
9
R
2
R
3
HN
O
HN
Bu
HN Me
NH
H 2 N
Bu
H 2 N
X = I, Br
R
1 = H, OMe, NO 2 , CN
amine = NH 3(aq)
15 products
Isolated yield: 69-96%
3 products
Isolated yield: 70-93%
a) Synthesis of amines and anilines
b) Cross-dehydrogenative coupling catalyzed by CuA NPs in glycerol
c) A
3 coupling catalyzed by CuA NPs in glycerol
d) CuA-catalyzed KA
2 multicomponent processes
O
O
+
X
N
H
+ R
1
[CuA NPs] (10 mol%)
10 mol% Ti(OiPr) 4
glycerol
100 °C, 12 h
or
4 products KA
2
Isolated yield: 66-82%
X = O, CH 2
R
1 = Ph, C 5 H 11
N
R
1
X
2.5 equiv. tBuOK
Scheme 8.14 CuA nanoparticles catalyzed C–N couplings and multicomponent reactions [33] (for
CuA, see Fig. 8.8)