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O
HgCl
2mol%Li
2
[PdCl
4
]
O
OMe
+
OMe
CuCl
2
,NaCl,HCl
O
2
,23°C
60 %
Heck 1968
Scheme 1.3 Palladium-catalyzed arylation of alkenes using an organomercury
reagent.
10 mol % Pd(OAc)
2
10 mol % Cu(OAc)
2
+
PhH, AcOH
O
2
,80°C
45 %
Fujiwara and Moritani 1969
Scheme 1.4 Palladium-catalyzed direct coupling of arenes with alkenes.
0.1 mol % FeCl
3
n
-HexMgBr
n
-Hex
+
Br
THF, 0 °C
83 %
Kochi 1971
Scheme 1.5 Cross-coupling of Grignard reagents with C(sp
2
)-bromides.
I
1mol%PdCl
2
+
KOAc, MeOH, 120 °C
74 %
Mizoroki 1971
I
1mol%Pd(OAc)
2
+
NBu
3
,100°C
75 %
Heck 1972
Scheme 1.6 Pd-catalyzed coupling of alkenes with aryl iodides.
arylations has progressed enormously and these advances are discussed by
Upendra Sharma, Atanu Modak, Soham Maity, Arun Maji and Debabrata
Maiti in Chapter 12.
Building on Kharasch's cobalt-catalyzed cross-coupling reaction, Kochi
accomplished an iron-catalyzed reaction between C(sp
2
)-Br electrophiles
and Grignard reagents (Scheme 1.5).
29
In the same year, Mizoroki and co-workers presented a related reaction to
the one reported by Heck in 1968 that importantly did not require the use of
toxic arylmercury, -tin or -lead reagents. The C-C bond formation between
ethylene or monosubstituted alkenes and iodobenzene could be achieved
using catalytic amounts of PdCl
2
or heterogeneous Pd black (Scheme 1.6).
30
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