Chemistry Reference
In-Depth Information
Br
O
HO
+
Cu(OTf)
2
, Cs
2
CO
3
EtO
2
C
EtO
2
C
2.572
2.573
2.574
Scheme 2.168
Et
2
N
O
Et
2
N
O
I
HO
(CH
3
CN)
4
CuPF
6
,
Cs
2
CO
3
O
+
OMe
OMe
2.575
2.576
2.577
Scheme 2.169
OH
CuI, 1,10-phen
Cs
2
CO
3
O
I
OMe
OMe
2.578
2.579
Scheme 2.170
CuBr,
phosphazene base
S
I
HS
+
MeO
Cl
MeO
Cl
2.582
2.580
2.581
Scheme 2.171
SH
I
S
+
CuI,
n
-Bu
4
NBr, NaOH
Cl
Cl
2.585
2.583
2.584
Scheme 2.172
2.12.3 Ullmann Coupling
Over a century ago, Ullmann reported coupling reactions catalysed by metallic copper.
205,206
The harsh
conditions typically involved limited its applicability, but Ullmann's work ultimately stimulated the search
for milder conditions using copper catalysis. Both copper(I) and copper(II) salts can catalyse the coupling of
aryl halides with a range of heteroatom nucleophiles, including phenols (Scheme 2.168, 2.169),
207
alcohols
(Scheme 2.170),
208
thiols (Scheme 2.171, 2.172),
209
amines (Scheme 2.173),
210
anilines (Scheme 2.174)
211
and
N
-heterocycles (Scheme 2.175, 2.176).
212,213
