16
J. Oliver–Meseguer and A. Leyva–Pérez
9a-f
OR 2
O
Pd nanoparticles, NMP, 135 ºC,
KOAc (1.2 eq.), H 2 O (1% v:v)
X= Br, I
H
R 3
8a-l
X
OR 2
O
R 3
Me 3 SnR 4
R 4
R 5 B(OH) 2
R 5
Heck
Sonogashira
Stille
Suzuki
2a-b
10a-g
11a-o
12a-b
13a-c
14a
15a-b
R 1
R 1
R 1
R 1
R 1
X
R
1
R
2
/ R
3
/ R
4
/ R
5
Product
Pd (ppm)
TOF0
[a]
Yield (%)
[b]
I
p -COMe 8a
R
2
= n Bu 2a
9a
3
2.3·10
5
99
H 8b
R
2
= n Bu 2a
9b
30
1.2·10
4
99
R
3
= n Oct 10a
11a
300
2.0·10
3
73
R
3
= Ph 10b
11b
300
7.2·10
3
83
R
5
= Ph 14a
15a
30
3.2·10
3
68
p -Br 8c
R
2
= n Bu 2a
9c
300
3.6·10
3
99
R
3
= n Oct 10a
11c
300
3.1·10
3
99
p -OMe 8d
R
2
= n Bu 2a
9d
300
3.2·10
3
99
R
2
= 2-Ethylhex 2b
9e
3
8.8·10
4
99
Br
p -COH 8e
R
3
= n Oct 10a
11d
3
2.0·10
5
99
R
3
= Ph 10b
11e
300
8.4·10
3
99
o -COH 8f
R
4
= n Bu 12a
13a
30
8.2·10
3
91
p -COMe 8g
R
2
= n Bu 2a
9a
300
3.1·10
4
99
R
3
= Ph 10b
11f
300
1.8·10
4
99
R
3
= n Oct 10a
11g
300
2.1·10
3
99
R
3
= n Oct 10a
11g
0
-
< 5
R
4
= n Bu 12a
13b
3
2.0·10
5
70
[c]
R
4
= n Bu 12a
13b
0
-
< 5
R
4
= Ph 12b
13c
3
7.9·10
4
44
R
5
= Ph 14a
15b
0.3
1.0·10
5
61
[c]
H 8h
R
2
= n Bu 2a
9b
300
8.8·10
2
64
R
3
= n Oct 10a
11a
300
5.2·10
3
99
R
3
= m- tol 10c
11h
300
6.6·10
3
99
R
3
= o- tol 10d
11i
300
1.2·10
3
96
R
3
= p- anisole 10e
11j
300
2.4·10
3
99
R
3
= o- anisole 10f
11k
300
2.0·10
3
94
R
3
= n Dodec 10g
11l
300
8.0·10
2
97
R
5
= Ph 14a
15a
30
7.6·10
3
87
R
5
= Ph 14a
15a
0
-
< 5
p -Me 8i
R
3
= n Oct 10a
11m
300
2.0·10
3
83
o,p -OMe-Napth 8j
R
3
= n Oct 10a
11n
300
4.9·10
3
99
o,o,p -Isoprop 8k
R
2
= 2-Ethylhex 2b
9f
300
1.1·10
4
35
[c]
p -OMe 8l
R
2
= n Bu 2a
9d
300
4.7·10
2
40
R
2
= n Bu 2a
9d
0
-
< 5
R
3
= Ph 10b
11j
300
2.8·10
2
50
a
b
c
Fig. 1.15 Reaction scheme for C–C coupling reactions catalyzed by Pd clusters formed in situ and
catalytic results a TOF 0 is calculated on the basis of total amount of palladium and indicated as
h −1 . b Product yields after 24 h. c Reaction temperature: 160 °C (Fig. from Ref. [5]. Copyright ©
2014 by John Wiley & Sons, Inc.)