J . Org. Chem. 2001, 66, 8677-8681
8677
C-N,7,8 and C-S9 bond-forming reactions. Moreover,
High ly Active, Air -Sta ble Ver sa tile
P a lla d iu m Ca ta lysts for th e C-C, C-N, a n d
C-S Bon d F or m a tion s via Cr oss-Cou p lin g
Rea ction s of Ar yl Ch lor id es
promising catalytic systems for the unactivated aryl
chlorides have been developed.3
-7,10,11
However, to the
best of our knowledge, no separable air-stable homoge-
neous catalysts12 have ever been reported involving
unactivated aryl chlorides and olefins, amines, and thiols.
This is partly due to the unstabilized active catalytic
species, and a mechanism that active catalytic species
are derived from the in situ reduction of Pd(II) by free
George Y. Li,* Gang Zheng, and Andrew F. Noonan
The DuPont Company, Central Research and Development
Department, Experimental Station, P.O. Box 80328,
Wilmington, Delaware 19880-0328
0
13
phosphine ligands to Pd , leading to difficulties in
separating and purifying these complexes.
Herein, we report the first example of simple, readily
accessible, and air-stable palladium(II) complexes (POPd,
POPd1, and POPd2) that serve as catalyst precursors
for the efficient cross-coupling reactions of aryl chlo-
rides in the processes of C-C, C-N, and C-S bond-
forming reactions to access a variety of such architec-
Received J uly 27, 2001
The transition-metal-catalyzed carbon-carbon and
carbon-heteroatom bond-forming reactions are impor-
tant fundamental transformations in synthetic chemis-
try.1 These reactions have been widely used for a variety
of cross-coupling reactions of aryl halides in the processes
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,2
3
4
5
6
of C-C (Suzuki, Kumada, Stille, Heck cross-coupling ),
(
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(
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(
1
(
1
(
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7
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1
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3 2
(12) (a) Pd(P(t-Bu) ) does not appear to be the active catalyst for
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(
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1
0.1021/jo010764c CCC: $20.00 © 2001 American Chemical Society
Published on Web 11/15/2001