356
D. Zou et al.
LETTER
Table 6 Cross-Coupling of Various N,N-Dialkylaminomethyltrifluoroborates with 4¢-Bromoacetophenonea (continued)
R2N
O
IIf (3 mol%)
Br
+
R2N
7b–e
BF3K
(3.0 equiv) Cs2CO3
THF–H2O (10:1; 0.25 M)
80 °C, 12 h
O
1a
8b–e
Entry
3
Trifluoroborate
Product
Isolated yield (%)
10
N
N
BF3K
O
7d
7e
8d
N
N
BF3K
4
30
O
8e
a All the reactions were carried out with 0.25 mmol of 4¢-bromoacetophenone and 0.375 mmol of potassium N,N-dialkylaminomethyltrifluoro-
borates.
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In conclusion, we have discovered a novel active catalyst–
cyclopalladated ferrocenylimine complex (IIf) for ami-
nomethylation of both aryl and heteroaryl halides contain-
ing varied functional groups with a variety of potassium
dialkylaminomethyltrifluoroborates. The novel coupling
methods described above will provide chemists with a
new catalytic system to introduce aminomethyl moiety
into a wide variety of molecules in a manner which is
complementary to existing procedures. Efforts toward the
further elaboration of this method, as well as applications
to complex molecule synthesis, are currently under way.
Acknowledgment
We are grateful to the Natural Science Foundation of China
(20772114) and Research Program of Fundamental and Advanced
Technology of Henan Province (113100531652) for financial sup-
port. The authors also would like to thank Dr. Yan Xia (Chemical
Research, Merck) for his comments and revision on the manuscript.
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Synlett 2011, No. 3, 349–356 © Thieme Stuttgart · New York