Transition-metal-catalyzed cross-couplings of aryl tosylates or mesylates with organoindium reagents

Article abstract of DOI:10.1055/s-0030-1258116

The first example of transition-metal-catalyzed cross-coupling reactions of aryl tosylates or mesylates with organoindium compounds is described. The desired carbon-carbon bond formation proceeds under mild conditions to generate the coupling products in

Full text of DOI:10.1055/s-0030-1258116

LETTER
1845
Transition-Metal-Catalyzed Cross-Couplings of Aryl Tosylates or Mesylates
with Organoindium Reagents
C
ross-Coupling
i
s
of
A
r
a
yl Sulfonate
n
s
with Organ
g
oindium
R
eagentsZhang,a Yong Luo,a Jie Wu*,a,b
a
Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433, P. R. of China
Fax +86(21)65641740; E-mail: jie_wu@fudan.edu.cn
b
State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences,
354 Fenglin Road, Shanghai 200032, P. R. of China
Received 16 March 2010
and 4). The yield was increased to 81% when
NiCl2(PCy3)2 was employed as the catalyst (Table 1, entry
5). A similar result was observed when the reaction was
performed at 80 °C (Table 1, entry 7). However, the reac-
tion was retarded at lower temperature (Table 1, entries 8
and 9). Subsequent examination of solvents revealed that
THF was the best choice, and the corresponding product
3a was afforded in almost quantitative yield (Table 1, en-
Abstract: The first example of transition-metal-catalyzed cross-
coupling reactions of aryl tosylates or mesylates with organoindium
compounds is described. The desired carbon–carbon bond forma-
tion proceeds under mild conditions to generate the coupling prod-
ucts in good yields.
Key words: aryl tosylate, aryl mesylate, cross-coupling reaction,
organoindium compound, transition metal
The organoindium reagent is regarded as an important al-
Table 1 Conditions Screening for Ni-Catalyzed Cross-Coupling
ternative in cross-coupling reactions due to its versatile Reaction of Aryl Tosylates 1a with Organoindium Reagent 2aa
chemistry and stability in air.1 Among the electrophiles
Ph
OTs
[Ni]/L
utilized in transition-metal-catalyzed cross-coupling reac-
tions, aryl arenesulfonates or mesylates have attracted
much attention recently2–9 due to their excellent stability
and easy availability. Moreover, the palladium-catalyzed
site-selective cross-coupling reactions could be expected
since aryl arenesulfonates are relatively unreactive com-
pared to the corresponding aryl halide and triflate counter-
parts.3j,10 Although some organometallic reagents (B, Zn,
Mg, Sn, Si, etc.) have been utilized in the coupling reac-
tions of aryl arenesulfonates or mesylates,2–8 to the best of
our knowledge, there are no reports using organoindium
compounds in such reactions. Herein, we disclose the first
example for the reactions of aryl arenesulfonates or mesy-
lates with organoindium compounds.
+
Ph3In
solvent
1a
2a
3a
Entry [Ni]
Ligand
Solvent Temp Time Yield
(°C)
100
100
100
100
100
120
80
(h)
48
48
48
48
48
18
48
48
48
24
24
24
24
24
24
(%)b
NR
60
55
46
81
83
81
27
4
1
2
NiCl2
–
DMA
DMA
DMA
NiCl2
NiCl2
NiCl2
PCy3
Pt-Bu3
3
4
Pt-Bu2Me DMA
5
NiCl2(PCy3)2 PCy3
NiCl2(PCy3)2 PCy3
NiCl2(PCy3)2 PCy3
NiCl2(PCy3)2 PCy3
NiCl2(PCy3)2 PCy3
NiCl2(PCy3)2 PCy3
NiCl2(PCy3)2 PCy3
NiCl2(PCy3)2 PCy3
NiCl2(PCy3)2 PCy3
NiCl2(PCy3)2 PCy3
NiCl2(PCy3)2 PCy3
DMA
DMA
DMA
DMA
DMA
THF
6
Since the C–O bond would undergo oxidative addition
during the reaction process and the nickel catalyst is ac-
tive for such a transformation,7,11 we thus selected nickel
catalyst for reaction development. At the outset, 2-naph-
thalenyl tosylate (1a) and triphenylindium (2a) were used
as the substrates. Results of this preliminary survey are
shown in Table 1. In an initial experiment, no reaction oc-
curred when NiCl2 (5 mol%) was employed in the reac-
tion as catalyst at 100 °C in DMA (Table 1, entry 1).
Parameters including catalysts, ligands, solvents, and
temperature were investigated subsequently. To our de-
light, the desired product was isolated in 60% yield when
PCy3 was utilized as a ligand in the reaction (Table 1, en-
try 2). The result could not be improved when Pt-Bu3 or
Pt-Bu2Me was used as a replacement (Table 1, entries 3
7
8
50
9
30
10
11
12
13
14c
15d
80
99
54
10
91
55
87
DMF
NMP
toluene
THF
80
80
80
80
THF
80
a Reaction conditions: tosylate 1a (0.50 mmol), InPh3 2a (0.50 mmol),
nickel catalyst (5 mol%), ligand (20 mol%), solvent (3.0 mL).
b Isolated yield based on aryl tosylates 1a.
SYNLETT 2010, No. 12, pp 1845–1848
x
x
.x
x
.2
0
1
0
c The reaction performed in the presence of NiCl2(PCy3)2 (1 mol%)
and PCy3 (4 mol%).
Advanced online publication: 30.06.2010
DOI: 10.1055/s-0030-1258116; Art ID: W04210ST
© Georg Thieme Verlag Stuttgart · New York
d The reaction performed in the presence of NiCl2(PCy3)2 (5 mol%)
and PCy3 (10 mol%).

1846
L. Zhang et al.
LETTER
pounds under the nickel-catalyzed conditions
[NiCl2(PCy3)2 (5 mol%), PCy3 (20 mol%), THF, 80 °C;
see Table 2]. For most cases, the desired coupling prod-
ucts were generated in good yields. For instance, 2-naph-
Table 2 Ni-Catalyzed Cross-Coupling Reactions of Aryl Sulfonate
1 with Organoindium Reagent 2
NiCl2(PCy3)2 (5 mol%)
OSO2R1
R3
PCy3 (20 mol%)
In(R3)3
R2
+
R2
THF, 80 °C
thalenyl
tosylate
(1a)
reacted
with
tri(4-
methoxyphenyl)indium (2b) leading to the corresponding
product 3b in 80% yield (Table 2, entry 2). Coupling
product 3c was afforded in 70% yield when tri(4-meth-
ylphenyl)indium was utilized as a replacement (Table 2,
entry 3). Substituted 2-naphthalenyl tosylate 1b or 1c was
examined as well in the reaction of triphenylindium (2a),
and the expected product 3d or 3e was generated in excel-
lent yield (Table 2, entries 4 and 5). 1-Naphthalenyl tosy-
late (1d) also worked well in the reaction of
triphenylindium (2a), giving rise to the desired product 3f
in almost quantitative yield (Table 2, entry 6). This nick-
el-catalyzed biaryl formation was found to be workable
with aryl tosylate 1e–g bearing acetyl, ester, and trifluo-
romethyl functional groups (Table 2, entries 7–9). How-
ever, only a trace amount of product was detected when
tert-butylphenyl tosylate (1h) was employed as the sub-
strate in the reaction of triphenylindium (2a, Table 2, en-
try 10). Naphthalen-1-yl benzenesulfonate (1i) was
workable as well in such a transformation (Table 2, entry
11). In addition, the reactions showed high efficiency
when aryl mesylates were utilized as substrates in the
reactions of organoindium compounds. For example, with
respect to 1- or 2-naphthalenyl mesylate 1j–m, organo-
indium compounds were suitable partners in this process,
and the desired products were isolated in good yields as
expected (Table 2, entries 12–17).
1
2
3
Entry Sulfonate
R3
Yield (%)a
OTs
1
2a Ph
3a 99
R
1a R = H
1a R = H
2
3
4
5
2b 4-MeOC6H4
2a 4-MeC6H4
2a Ph
3b 80
3c 70
3d 91
3e 99
1a R = H
1b R = C6H5
1c R = 4-FC6H4
2a Ph
OTs
6
7
2a Ph
3f 99
1d
R
OTs
2a Ph
3g 73
1e R = 4-COMe
1f R = 4-COOEt
8
9
2a Ph
2a Ph
2a Ph
3h 63
3i 50
–
1g R = 4-CF3
1h R = 4-t-Bu
OSO2Ph
10
Palladium-catalyzed reactions of aryl tosylates or mesy-
lates 1 with organoindium compounds were tested mean-
while (Scheme 1). After screening the reaction
conditions, we realized that in the presence of Pd(OAc)2
(5 mol%) and XPhos (10 mol%), the reactions of aryl to-
sylates 1 proceeded smoothly in THF at 80 °C to afford
the desired products 3 in good yields (Scheme 1, equation
1).
11
12
2a Ph
2a Ph
3f 73
3a 90
1i
OMs
R
1j R = H
1j R = H
However, aryl mesylates showed low reactivity under the
conditions (Scheme 1, equation 2).
13
14
15
16
2b 4-MeOC6H4
2a 4-MeC6H4
2a Ph
3b 60
3c 61
3j 88
3e 95
1j R = H
A possible mechanism was proposed meanwhile
(Scheme 2). We reasoned that after oxidative addition of
Ni(0) or Pd(0) to aryl sulfonate 1, the transmetallation of
intermediate A with organoindium reagent 2 would give
rise to intermediate B. Subsequently reductive elimination
occurred leading to the desired product 3 and Ni(0) or
Pd(0), which would re-enter the catalytic cycle.
1k R = 4-MeC6H4
1l R = 4-FC6H4
OMs
2a Ph
17
2a Ph
3f 83
In summary, we have developed the first example for tran-
sition-metal-catalyzed cross-coupling reactions of aryl to-
sylates or mesylates with organoindium compounds. The
desired carbon–carbon bond formation proceeds under
mild conditions to generate the coupling products in good
yields. Using aryl sulfonates as substrates for other trans-
formations is under investigation, and the results will be
reported in due course.
1m
a Isolated yields based on arylsulfonate 1.
tries 10–13). Decreasing the amount of catalyst or ligand
diminished the product yield (Table 1, entries 14 and 15).
Encouraged by this result, we started to investigate the
scope of this reaction. Thus, various aryl arenesulfonates
1 were employed in the reactions of organoindium com-
Synlett 2010, No. 12, 1845–1848 © Thieme Stuttgart · New York

LETTER
Cross-Couplings of Aryl Sulfonates with Organoindium Reagents
1847
Pd(OAc)2 (5 mol%)
Ph
OTs
XPhos (10 mol%)
InPh
+
+
3
(1)
(2)
THF, 80 °C
R
R
R
1a R = H
1c R = 4-FC6H4
2a
3a R = H, 93%
3e R = 4-FC6H4, 80%
Pd(OAc)2 (5 mol%)
XPhos (10 mol%)
Ph
OMs
InPh
3
THF, 80 °C
R
1k R = 4-MeC6H4
1l R = 4-FC6H4
2a
3j R = 4-MeC6H4, 30%
3e R = 4-FC6H4, 43%
Scheme 1 Pd-Catalyzed cross-coupling reactions of aryl sulfonate 1 with organoindium reagent 2
A. S. C.; Kwong, F. Y. J. Org. Chem. 2008, 73, 7731.
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R2
OSO2R1
M (0)
3
R2
reductive
elimination
oxidative
addition
1
II
II
M
M
OSO2R1
R3
R2
R2
B
A
M: Ni or Pd
In(R3)3
transmetallation
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2
Scheme 2 Possible mechanism for the cross-coupling reactions of
aryl sulfonate 1 with organoindium reagent 2
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synlett.
Acknowledgment
Financial support from the National Natural Science Foundation of
China (20972030) and the Science & Technology Commission of
Shanghai Municipality (09JC1404902) is gratefully acknowledged.
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