A highly active and general catalyst for the stille coupling reaction of unreactive aryl, heteroaryl, and vinyl chlorides under mild conditions

Article abstract of DOI:10.1002/adsc.201300075

A β-diketiminatophosphane-palladium complex was found to act as an efficient and general catalyst in the Stille coupling reaction of various aryl and heteroaryl chlorides with organostannanes. The results show that this catalytic system allows for the use of less reactive substrates such as deactivated or sterically hindered aryl chlorides. A catalyst loading of 0.5 mol% was sufficient to achieve excellent performance under relatively mild reaction conditions. Furthermore, the scope of catalyst was extended to the coupling of vinyl chlorides. Copyright

Full text of DOI:10.1002/adsc.201300075

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DOI: 10.1002/adsc.201300075
A Highly Active and General Catalyst for the Stille Coupling
Reaction of Unreactive Aryl, Heteroaryl, and Vinyl Chlorides
under Mild Conditions
Dong-Hwan Lee,+a Yingjie Qian,+a Ji-Hoon Park,a Jong-Suk Lee,a Sang-Eun Shim,a
and Myung-Jong Jina,*
a
Department of Chemical Science and Engineering, Inha University, Incheon 402-751, South Korea
Fax : (+82)-32-872-0939; e-mail: mjjin@inha.ac.kr
+
These authors contributed equally to this work.
Received: January 26, 2013; Revised: April 7, 2013; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201300075.
Abstract:
A
b-diketiminatophosphane-palladium
ysis, make the coupling of aryl chlorides much more
difficult.[5] Only few catalysts have been reported in
this area.[6] Furthermore, most of the reactions always
have some disadvantages including high catalyst load-
ings, long reaction times, and harsh reaction condi-
tions. In particular, successful examples using deacti-
vated aryl chlorides are quite rare. Therefore, there is
growing interest in the development of catalysts that
are able to work in the coupling of the unreactive
substrates under mild conditions. We have recently re-
ported b-diketiminatophosphane-palladium catalysts 2
for various cross-coupling reactions of aryl chlorides.[7]
In a continuing effort to explore their catalytic poten-
tial, we herein describe the use of Pd catalyst 2a in
the Stille coupling reaction of less reactive aryl chlor-
ides.
complex was found to act as an efficient and gener-
al catalyst in the Stille coupling reaction of various
aryl and heteroaryl chlorides with organostannanes.
The results show that this catalytic system allows
for the use of less reactive substrates such as deacti-
vated or sterically hindered aryl chlorides. A cata-
lyst loading of 0.5 mol% was sufficient to achieve
excellent performance under relatively mild reac-
tion conditions. Furthermore, the scope of catalyst
was extended to the coupling of vinyl chlorides.
À
Keywords: aryl chlorides; C C coupling; homoge-
neous catalysis; palladium; Stille reaction
b-Diketiminatophosphane Pd complexes 2 were
conveniently synthesized from acetylacetone by the
The palladium-catalyzed Stille coupling reaction of following sequence: (i) condensation of acetylacetone
organohalides with organostannane reagents has and primary amines under microwave or conventional
proven to be a valuable and powerful tool for the for- heating, (ii) deprotonation of 1 with EtOTl in THF at
mation of carbon-carbon bonds.[1] This coupling has 0–208C, (iii) treatment with Pd
2ACHTNUGTRNE(UGN m-Cl)2Me2L2 (L=
been employed in the synthesis of biaryl compounds PPh3 or PEt3)[8] (Scheme 1). It is noteworthy that the
that are important intermediates in natural products, complexes have considerable air and moisture stabili-
polymers, and pharmaceuticals.[2] A number of effec- ty. They were characterized by elemental analysis,
tive palladium catalytic systems have been developed 1H NMR, 13C NMR, and 31P NMR spectroscopy.
for the Stille coupling. Generally, phosphine ligands
in combination with palladium precursors provide ef- ed 2-chloroanisole with tributylphenylstannane be-
fective catalysts for the reaction. cause catalysts that can activate this aryl chloride
Initial studies focused on the coupling of deactivat-
A major limitation of the coupling is that it is nec- would be expected to be effective with a wide range
essary to use reactive aryl iodide or bromide sub- of aryl chlorides. At first, we performed this reaction
strates.[3] The use of aryl chlorides would be very de- in the presence of 0.5 mol% of 2a and 2.0 equiv. of
sirable for industrial applications because they are CsF in THF at 508C. The coupling proceeded very
cheaper and more widely available than their bromide well to afford the desired product in 92% yield after
or iodide counterparts.[4] However, the strong C Cl 5 h (Table 1, entry 1). The activity obtained with 2a is
À
bonds, which disfavour oxidative addition in the catal- remarkably superior to any previously reported re-
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ortho-methyl groups in the diketimine ligand exert
beneficial electronic and steric effects in enhancing
the reactivity and therefore giving a more active cata-
lyst. It is supposed that the bulky diketimine and elec-
tron-rich triethylphosphane of 2a cooperatively pro-
mote the oxidative addition and reductive elimina-
tion. With the optimized conditions in hand, we ex-
plored the coupling of various aryl chlorides with
aryl- and vinylstannanes. The reactions of activated 4-
chloro-acetophenone, 1-chloro-2-nitrobenzene, and
chlorobenzene with tributylphenylstannane provided
Scheme 1. Synthesis of b-diketiminatophosphane-Pd cata-
lysts 2.
sults on the Stille coupling. A catalyst loading as low biaryls in excellent yields (Table 2, entries 1–3). Grati-
as 0.1 mol% was shown to be effective (Table 1, fyingly, comparable catalytic activities were observed
entry 2). It was possible to achieve this coupling even in the couplings of deactivated aryl chlorides possess-
at room temperature, though a prolonged reaction ing electron-donating substituents (Table 2, entries 4–
time was required (Table 1, entry 3). The solvent 6). 1-Chloronaphthalene also reacted very well
effect on the activity was examined with different sol- (Table 2, entry 7). Couplings of aryl chlorides contain-
vents because the selection of the solvent is some- ing a free amino or hydroxy group are typically diffi-
times crucial in the coupling reactions. When the re- cult to accomplish.[6] It is therefore noteworthy that
action was conducted in toluene, acetonitrile, NMP, catalyst 2a is effective for unprotected 2-chloroaniline
DME and 1,4-dioxane instead of THF, the catalytic and 4-chlorophenol (Table 2, entries 8 and 9). More-
activity was reduced under the same conditions over, satisfactory levels of activity were observed for
(Table 1, entries 4–8). By screening different bases in- the couplings with electron-rich arylstannanes
cluding KF, K3PO4, Na2CO3, and Cs2CO3 (Table 1, en- (Table 2, entries 10–14). It should be noted that the
tries 9–12), CsF was found to be the best one.
sterically
hindered
2-chloro-1,3-dimethylbenzene
As expected, catalysts 2b and 2c exhibited inferior could be coupled well in 81% yield, although some-
catalytic activities compared with 2a (Table 1, en- what elevated temperatures were required (Table 2,
tries 13 and 14). This indicates that the strong elec- entry 15). The Stille reaction is especially useful for
tron-donating triethylphosphane ligand increases the the preparation of arylalkenes. Satisfactory results
electron density on the palladium center,[9] facilitating were obtained in the reactions of 4-chloroanisole and
the rate-limiting oxidative addition of the active Pd 2-chloro-1,3-dimethylbenzene with tributylvinylstanne
species to the less reactive aryl chlorides. In addition, (Table 2, entries 16 and 17). Regardless of the sub-
Table 1. Stille coupling of 2-chloroanisole with tributylphenylstannane.[a]
Entry
2 [mol%]
Solvent
Base
Time [h]
Yield [%][b]
1
2a (0.5)
2a (0.1)
2a (1.0)
2a (0.5)
2a (0.5)
2a (0.5)
2a (0.5)
2a (0.5)
2a (0.5)
2a (0.5)
2a (0.5)
2a (0.5)
2b (0.5)
2c (0.5)
THF
THF
THF
toluene
acetonitrile
NMP
DME
1,4-dioxane
THF
THF
THF
THF
THF
CsF
CsF
CsF
CsF
CsF
CsF
CsF
CsF
5
92 (91)
84
81
67
72
2
12
18
5
5
5
5
5
5
5
5
5
5
5
3[c]
4
5
6
7
8
86
89 (86)
75 (71)
69
54
45
51
62
79
9
KF
10
11
12
13
14
K3PO4
Na2CO3
Cs2CO3
CsF
THF
CsF
[a]
Reaction conditions: 2-chloroanisole (1.0 mmol), tributylphenylstannane (1.1 mmol), base (2.0 mmol), solvent (2.0 mL)
and a catalytic amount of 2, NMP=N-methylpyrrolidine, DME=dimethoxyethane.
GC yield was determined using n-dodecane as an internal standard. Isolated yield is given in parenthesis.
Reaction was performed at room temperature.
[b]
[c]
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A Highly Active and General Catalyst for the Stille Coupling Reaction
Table 2. Stille coupling of aryl chlorides with organostannanes.[a]
Entry
1
Aryl chloride
Organostannane
Time [h]
3
Yield [%][b]
91
2
3
93
3
4
5
4
4
4
90
89
86
6
7
6
4
91
87
8
9
6
5
85
89
10
8
87
11
12
13
14
8
6
8
8
83
91
83 (80)
87
15c
16
12
6
81
85
78
17[c]
12
[a]
Reaction conditions: aryl chloride (1.0 mmol), organostannane (1.1 mmol), CsF (2.0 mmol), 508C, and 2a (0.5 mol%).
Isolated yield.
Reaction was performed at 808C.
[b]
[c]
stituents, most of the couplings were very clean and chlorides give low conversions and remain challeng-
efficient under mild heating. ing. Therefore, development of effective catalysts for
The Stille coupling of heteroaryl halides is remarka- this useful reaction is an important mission in the
bly useful in the pharmaceutical industry since biolog- field.
ically active molecules are accessed through this
We attempted the coupling of different heteroaryl
methodology.[10] However, the reactions of heteroaryl chlorides with arylstannanes in the presence of
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Table 3. Stille coupling of heteroaryl and vinyl chlorides with organostannanes.[a]
Entry
Heteroaryl/vinyl chloride
Organostannane
Time [h]
Yield [%][b]
1
2
4
4
87
94
3
4
83
4
5
6
4
5
6
86
82
81
7
8
8
8
89
86
9
8
8
87
78
10
11
12
5
4
84
92
13
14
15
6
6
6
6
76
82
87
79
16
[a]
Reaction conditions: aryl chloride (1.0 mmol), organostannane (1.1 mmol), CsF (2.0 mmol), 508C, and 2a (0.5 mol%).
Isolated yield.
[b]
0.5 mol% of 2a at 508C (Table 3). Chloropyridines (Table 3, entries 9 and 10). Chlorothiophenes are
were coupled to tributylphenylstannane in high yields problematic substrates due to the strong affinity of
(Table 3, entries 1 and 2). The electronic property of the sulfur for Pd.[11] 3-Chlorothiophene coupled effec-
the substituents in the arylstannanes had a small influ- tively with tributylphenylstannane in 84% yield
ence to the formation of biaryls (Table 3, entries 3–6). (Table 3, entry 11). An aldehyde functional group was
2-Chloroquinoline and 1-chloroisoquinoline could be tolerated under the present conditions (Table 3,
successfully transformed to the desired products entry 12). This catalyst was also active for the reaction
(Table 3, entries 7 and 8). 2-Chloro-3-methylpyridine of unprotected 5-chloroindole with tributyl
was also found to be a suitable coupling partner stannane (Table 3, entry 13).
ACHTUNGTRENUN(NG o-tolyl)-
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A Highly Active and General Catalyst for the Stille Coupling Reaction
Table 4. Stille coupling of various aryl and vinyl chlorides with organostannanes.[a]
Entry Aryl chloride
Organostannane Product
Temperature [8C] Time [h] Yield [%][b]
1[c]
70
8
72
2[c]
70
50
8
5
81
86
3
4
70
8
76
5
6
70
70
6
6
79
73
7
8
70
70
8
8
68
82
9
70
70
8
75
71
10[d]
10
[a]
Reaction conditions: aryl chloride (1.0 mmol), organostannane (1.3 mmol), CsF (2.0 mmol), and 2a (0.5 mol%).
Isolated yield.
Organostannane (2.6 mmol) and 2a (1.0 mol%).
[b]
[c]
[d]
Organostannane (1.4 mmol) and 2a (1.0 mol%).
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Next, we tested catalyst 2a in the very important primarily evaluated with 4–8 mol% of the catalysts at
Stille coupling of vinyl chlorides.[6b,12] Gratifyingly, 1- 30–808C. Very recently, Ma and co-workers used
chlorocycloalkenes could be coupled to tributyl
ACHTUNGTRENNUNG
ACHTUNGTREN(NUGN o-tol- 1 mol% of palladacycle catalysts for the coupling of
yl)stannane in good yields (Table 3, entries 14–16). aryl chlorides with tributylstannylpyridine.[6g] The re-
Previously, long reaction time, high temperature, and actions require a high temperature of 1108C to obtain
high catalyst loading (40 h, 1008C, and 3.5 mol%) the desired products in high yields. Lipshulz and co-
were required for this substrate.[6b]
workers also described mild Stille couplings in
Encouraged by the above success, we subsequently water.[6h] Although 2–4 mol% of their catalytic system
studied the scope and generality of this process and was quite effective for the reaction of activated aryl
its applicability for synthetic problems. As illustrated chlorides at room temperature to 608C, the applica-
in Table 4, an array of functionalized aryl and vinyl tion to vinyl chlorides and deactivated aryl chlorides
chlorides underwent effective coupling reactions with such as 2-chloroanisole seems to be difficult to accom-
organostannanes to affored potentially valuable prod- plish. In contrast, our present catalyst 2a showed both
ucts. Quite interestingly, the effectiveness of catalyst high activity and excellent functional group compati-
2a was observed in a one-pot double coupling of bility. Regardless of the substituent, most of the cou-
a sterically hindered aryl dichloride and an arylstan- pling reactions of (hetero)aryl chlorides and vinyl
nane (Table 4, entry 1). This method would be desira- chlorides were very efficient in the presence of only
ble for the preparation of arylated biphenyls.[13] Hin- 0.5 mol% catalyst at low temperature of 508C.
dered and electron-rich 2,6-dichloroaniline having
To the best of our knowledge, catalyst 2a is one of
a free amino group was also combined with a hindered the most general and active catalysts reported so far
arylstannane to provide the dicoupled product in 81% for the coupling of both (hetero)aryl chlorides and
yield (Table 4, entry 2).
vinyl chlorides. These results represent a significant
We have now extended this process to aryl chlor- advancement in the Stille reaction. Pd complex 2a has
ides containing electrophilic functional groups such as a unique structural feature containing both electron-
ketones and a, b-unsaturated ester. For examples, 3- rich triethylphosphane and bulky diketimine moieties
(2-chlorophenyl)cyclohexanone and 3-(2-chloro-3- on the palladium center. Although the mechanism of
methylphenyl)-1,3-diphenyl-1-propanone
coupled 2a-catalyzed coupling is not obvious, the high catalytic
with 2-(tributylstannyl)pyridine in good yields activity is probably attributed to the enhanced nucleo-
(Table 4, entries 3 and 4). Similarly, this method was philicity of the active palladium(0) species which un-
À
effective for (2E)-3-(2-chlorophenyl)-2-propenoate dergo Ar Cl bond cleavage in the rate-limiting oxida-
(Table 4, entries 5–7). This compound can be used as tion step.
a precursor for the facile construction of bicyclic skel-
In summary, the present work has resulted in the
development of an excellent catalyst 2a for the Stille
etons.[14]
It was also possible to couple functionalized vinyl coupling reaction. We have demonstrated that b-
chloride derivatives under our standard protocol. Ex- diketiminatophosphane-palladium complex 2a serves
AHCTUNGTRENNUNG
amples of this class of compounds, ethyl (E)-3-(2- as an active catalyst for the Stille coupling reaction.
chlorocyclopent-1-enyl)-2-propenoate and 4-chloro-7- Various aryl, heteroaryl, and vinyl chlorides coupled
methoxy-2H-1-benzopyran-2-one could all be trans- effectively with organostannanes under mild condi-
formed to the expected products (Table 4, entries 8 tions. We envision that extensions of this catalyst will
and 9). The later coupling was proven to be useful for permit the development of superior catalytic systems.
the synthesis of 4-arylcoumarins.[15] In particular, we
were pleased to observe that this catalytic system
allows for a facile synthesis of biologically active mol-
ecules. 3-Chlorocholesta-3,5-diene[16] was reacted with
tributyl(2,5-dimethoxyphenyl)stannane to give the
Experimental Section
target compound in 71% yield (Table 4, entry 10).
General Procedure for Stille Coupling Reactions
The use of vinyl chlorides allows for structural diversi-
Aryl chloride (1.0 mmol), organostannane (1.1 mmol), CsF
(2.0 mmol), and a catalytic amount of Pd complex
ty of the products as well as expanding the scope of
Stille reactions.
2
(0.5 mol%) were added in THF (2.0 mL). The reaction mix-
ture was stirred at 508C and monitored by GC/GC-MS.
After completion of the reaction, THF solvent was finally
evaporated under reduced pressure. The residue was treated
with diethyl ether (10 mL) and water (5 mL). The layers
were separated and the aqueous phase was extracted with
diethyl ether (2ꢁ10 mL). The combined organic phases
were washed with brine (10 mL), dried with MgSO4, and
We previously demonstrated that b-diketoiminato-
phosphane Pd complexes act as highly active catalysts
in the Stille reaction of (hetero)aryl chlorides.[6e]
However, the catalysts were not applied to the cou-
pling of vinyl chlorides due to their unsatisfactory per-
formance. Recently, the efficient reaction of aryl
chlorides using Pd-PEPPSI catalysts was described by
Organ and co-workers.[6f] Heteroaryl chlorides were concentrated in vacuo. The crude product was purified by
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short column chromatography on silica gel to afford the de-
sired product.
dron Lett. 2010, 51, 6886; n) E. Flçistrup, P. Goede, R.
Strçmberg, J. Malm, Tetrahedron Lett. 2011, 52, 209;
o) H. Germain, C. S. Harris, H. Lebraud, Tetrahedron
Lett. 2011, 52, 6376; p) L. E. Polander, A. S. Romanov,
S. Barlow, D. K. Hwang, B. Kippelen, T. V. Timofeeva,
S. R. Marder, Org. Lett. 2012, 14, 918.
Acknowledgements
[4] a) A. F. Littke, G. C. Fu, Angew. Chem. 2002, 114,
4350; Angew. Chem. Int. Ed. 2002, 41, 4176; b) A. F.
Littke, L. Schwarz, G. C. Fu, J. Am. Chem. Soc. 2002,
124, 6343; c) C. Wolf, R. Lerebours, J. Org. Chem.
2003, 68, 7551; d) R. B. Bedford, C. S. J. Cazin, D.
Holder, Coord. Chem. Rev. 2004, 248, 2283.
[5] V. V. Grushin, H. Alper, Activation of Unreactive
Bonds and Organic Synthesis, Springer, Berlin, 1999.
[6] a) A. F. Littke, L. Schwarz, G. C. Fu, J. Am. Chem. Soc.
2002, 124, 6343; b) W. Su, S. Urgaonkar, A. P.
McLaughlin, G. Verkade, J. Am. Chem. Soc. 2004, 126,
16433; c) J. R. Naber, S. L. Buchwald, Adv. Synth.
Catal. 2008, 350, 957; d) M.-J. Jin, D.-H. Lee, Angew.
Chem. 2010, 122, 1137; Angew. Chem. Int. Ed. 2010, 49,
1119; e) D.-H. Lee, A. Taher, W.-S. Ahn, M.-J. Jin,
Chem. Commun. 2010, 46, 478; f) M. Dowlut, D.
Mallik, M. G. Organ, Chem. Eur. J. 2010, 16, 4279;
g) G. Ma, Y. Leng, Y. Wu, Y. Wu, Tetrahedron 2013, 69,
902; h) G.-p. Lu, C. Caib, B. H. Lipshutz, Green Chem.
2013, 15, 105.
[7] a) D.-H. Lee, J.-Y. Jung, M.-J. Jin, Chem. Commun.
2010, 46, 9046; b) D.-H. Lee, M.-J. Jin, Org. Lett. 2011,
13, 252; c) D.-H. Lee, A. Taher, S. Hossain, M.-J. Jin,
Org. Lett. 2011, 13, 5540; d) D.-H. Lee, M.-J. Jin, Adv.
Synth. Catal. 2011, 353, 3090.
[8] F. T. Ladipo, G. K. Anderson, Organometallics 1994, 13,
303.
[9] a) S.-L. Ku, X.-P. Hui, C.-A. Chen, Y.-Y. Kuo, H.-M.
Gau, Chem. Commun. 2007, 3847; b) G. C. Fu, Acc.
Chem. Res. Acc. Chem. Res 2008, 41, 1555.
[10] a) A. F. Pozharskii, A. T. Spldartenko, A. Katritzky,
Heterocycles in Life and Society, Wiley, New York,
1997; b) E. Tyrell, P. Brookes, Synthesis 2004, 469.
[11] I. J. S. Fairlamb, Chem. Soc. Rev. Chem. Soc. Rev 2007,
36, 1036.
[12] R. N. Hanson, E. McCaskill, P. Tongcharoensirikul, R.
Dilis, D. Labaree, R. B. Hochberg, Steroids 2012, 77,
471.
[13] J. He, J. L. Crase, S. H. Wadumethrige, K. Thakur, L.
Dai, S. Zou, R. Rathore, C. S. Hartley, J. Am. Chem.
Soc. 2010, 132, 13848.
[14] H. Urabe, K. Suzuki, F. Sato, J. Am. Chem. Soc. 1997,
119, 10014.
This work was supported by a National Research Foundation
of Korea Grant funded by the Korean Government (2012-
003212) and an Inha University Research Grant (2013).
References
[1] For reviews, see; a) J. K. Stille, Pure Appl. Chem. 1985,
57, 1771; b) M. Pereyre, J. P. Quintard, A. Rahm, Tin in
Organic Synthesis Butterworth, London 1987; c) V.
Farina, V. Krishnamurthy, W. J. Scott, The Stille Reac-
tion, John Wiley & Sons, New York, 1998; d) T. N.
Mitchell, Metal-Catalyzed Cross-Coupling Reactions,
Wiley-VCH, Weinheim, 2004; e) P. Espinet, A. M.
Echavarren, Angew. Chem. 2004, 116, 4808; Angew.
Chem. Int. Ed. 2004, 43, 4704; f) C. Valente, S. Calim-
siz, K. H. Hoi, D. Mallik, M. Sayah, M. G. Organ,
Angew. Chem. 2012, 124, 3370; Angew. Chem. Int. Ed.
2012, 51, 3314.
[2] a) G. Bringmann, D. Menche, Acc. Chem. Res. 2001, 34,
615; b) G. Bringmann, Y. Reichert, V. V. Kane, Tetrahe-
dron 2004, 60, 3539; c) T. W. Wallace, Org. Biomol.
Chem. 2006, 4, 3197; d) T. C. Roberts, P. A. Smith, R. T.
Cirz, R. E. Romesberg, J. Am. Chem. Soc. 2007, 129,
15830; e) W. Yue, A. Lv, J. Gao, W. Jiang, L. Hao, C.
Li, Y. Li, L. E. Polander, S. Barlow, W. Hu, S. D. Motta,
F. Negri, S. R. Marder, Z. Wang, J. Am. Chem. Soc.
2012, 134, 5770.
[3] a) W.-S. Kim, H.-J. Kim, C.-G. Cho, Tetrahedron Lett.
2002, 43, 9015; b) S. P. H. Mee, V. Lee, J. E. Baldwin,
Angew. Chem. 2004, 116, 1152; Angew. Chem. Int. Ed.
2004, 43, 1132; c) D. Olsson, P. Nilsson, M. E. Mas-
naouy, O. F. Wendt, Dalton Trans. 2005, 1924; d) J.-H.
Li, Y. Liang, D.-P. Wang, W.-J. Liu, Y.-X. Xie, D.-L.
Yin, J. Org. Chem. 2005, 70, 2832; e) S. P. H. Mee, V.
Lee, J. E. Baldwin, Chem. Eur. J. 2005, 11, 3294; f) W.
Shi, C. Liu, Z. Yu, A. Lei, Chem. Commun. 2007, 2342;
g) J. Hꢂmmerle, M. Schnꢃrch, P. Stanetty, Synlett 2007,
2975; h) W.-J. Zhou, K.-H. Wang, J.-X. Wang, Adv.
Synth. Catal. 2009, 351, 1378; i) G. Kerric, E. L. Grog-
nec, F. Zammattio, M. Paris, J.-P. Quintard, J. Orgno-
met. Chem. 2010, 695, 103; j) Y. Yabe, T. Maegawa, Y.
Monguchi, H. Sajiki, Tetrahedron 2010, 66, 8654; k) R.
Chotima, T. Dale, M. Green, T. W. Hey, C. L. McMul-
lin, A. Nunns, A. G. Orpen, I. V. Shishkov, D. F. Wass,
R. L. Wingad, Dalton Trans. 2011, 40, 5316; l) A. Pal,
R. Ghosh, N. N. Adarsh, A. Sarkar, Tetrahedron 2010,
66, 5451; m) J. Sꢂvmarker, J. Lindh, P. Nilsson, Tetrahe-
[15] Y. Li, Z. Qi, H. Wang, X. Fu, C. Duan, J. Org. Chem.
2012, 77, 2053.
[16] J. Pan, X. Wang, Y. Zhang, S. L. Buchwald, Org. Lett.
2011, 13, 4974.
Adv. Synth. Catal. 0000, 000, 0 – 0
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COMMUNICATIONS
8 A Highly Active and General Catalyst for the Stille
Coupling Reaction of Unreactive Aryl, Heteroaryl, and
Vinyl Chlorides under Mild Conditions
Adv. Synth. Catal. 2013, 355, 1 – 8
Dong-Hwan Lee, Yingjie Qian, Ji-Hoon Park,
Jong-Suk Lee, Sang-Eun Shim, Myung-Jong Jin*
8
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