1 Ligand-Free Sub-Nanometer Metal Clusters in Catalysis
29
N
O
4
clusters (0.15 mol%): 67%
Cu-diamine (5 mol%): 80%
S
OH
N
O
5
N
O
S
N
N
5
H
N
O
NuH
+
R
R I
3
clusters (0.02 mol%): 63%
Cu-diamine (5 mol%): 97%
5
clusters (0.15 mol%): 62%
Cu-diamine (5 mol%): 99%
6
clusters (0.15 mol%): 62%
Cu-diamine (5 mol%): 96%
7
clusters (0.15 mol%): 65%
Cu-diamine (5 mol%): 51%
8
clusters (0.15 mol%): 56%
Cu-diamine (10 mol%): 97%
9
clusters (0.05 mol%): 91%
Cu-diamine (5 mol%): <5%
10
clusters (0.5 mol%): 52%
Cu-diamine (5 mol%): 68%
Cu cluster (0.02-1 mol%)
NMP or DMF (0.5 M), 135 ºC, 24 h
(1.5 mmol) (1 mmol)
S
CN
P
NC
Br
11
clusters (0.5 mol%): 62%
Cu-diamine (5 mol%): 76%
P
NH 2
K 3 PO 4 or K 2 CO 3 (2 mmol)
5
N
12
clusters (1 mol%): 71%
Cu-diamine (5 mol%): 77%
13
clusters (0.5 mol%): 51%
Cu-diamine (5 mol%): 39%
14
clusters (0.2 mol%): 81%
Cu-diamine (5 mol%): 63%
15
clusters (0.03 mol%): 41%
Cu-diamine (10 mol%): 53%
16
clusters (0.15 mol%): 45%
Cu-diamine (0.5 mol%): 35%
17
clusters (0.15 mol%): 60%
Cu-diamine (5 mol%): <5%
O
Br
O
Cl
O
N
H
O
CF 3
N
H
18
clusters (0.03 mol%): 74%
Cu-diamine (20 mol%): 90%
O
H
O
Nu
Cu-diamine 1 mol%
Cu clusters 0.03 mol%
Cu-diamine 0.05 mol%
Fig. 1.27 Scope of the Cu cluster-catalyzed cross-coupling reactions. Isolated yields. The new
bonds are in bold. For comparison, the values with Cu–diamine catalysts are also given, reaction
conditions: substrates (1 mmol), CuI (5–20 mol%), N,N–methyl ethylenediamine (10–40 mol%),
K 3 PO 4 (2 mmol), anhydrous toluene or dioxane (0.25 M), nitrogen atmosphere, 110 °C, 24 h. The
inset shows the kinetics for the Goldberg coupling between the iodobenzene and the amide under
typical reaction conditions for diamine-assisted coupling and the conditions reported (Fig. from
Ref. [54]. Copyright © 2015 by American Chemical Society)