Palladium-catalyzed desulfitative Sonogashira-Hagihara cross-couplings of arenesulfonyl chlorides and terminal alkynes

Article abstract of DOI:10.1002/adsc.200404146

For the first time, conditions have been found for the palladium-catalyzed desulfitative carbon-carbon cross-coupling of arenesulfonyl chlorides with aryl- and alkylacetylenes. Pd₂(dba)₃/P(t-Bu)₃ and CuI provide the best c

Full text of DOI:10.1002/adsc.200404146

FULL PAPERS
Palladium-Catalyzed Desulfitative Sonogashira--Hagihara
Cross-Couplings of Arenesulfonyl Chlorides and Terminal
Alkynes
Srinivas Reddy Dubbaka, Pierre Vogel*
Laboratory of Glycochemistry and Asymmetric Synthesis, Swiss Federal Institute of Technology (EPFL), BCH,
1015 Lausanne, Switzerland
Fax: (þ41)-21-693-9375, e-mail: pierre.vogel@epfl.ch
Received: May 24, 2004; Accepted: August 23, 2004
Dedicated to Joe Richmond on the occasion of his 60th birthday.
Abstract: For the first time, conditions have been Keywords: alkynes; arenesulfonyl chlorides; CÀC
found for the palladium-catalyzed desulfitative car- cross coupling; homogeneous catalysis; palladium;
bon-carbon cross-coupling of arenesulfonyl chlorides tri(t-butyl)phosphine ligand
with aryl- and alkylacetylenes. Pd (dba) /P(t-Bu)
2
3
3
and CuI provide the best catalyst for reactions in re-
fluxing THFand in the presence of K CO .
2
3
[
16]
Introduction
chlorides have been engaged in carbon-vinylation,
[
17]
[18]
carbon-carbonylation,
and homo-couplings.
Re-
Palladium-catalyzed cross-coupling reactions are ex- cently, we have disclosed the palladium-catalyzed Stille,
[
1,2]
[19]
[20]
tremely useful synthetic tools.
The typical Sonoga- carbonylative Stille, Suzuki–Miyaura and Heck–
[21]
shira–Hagihara reaction is applied for the coupling of Mizoroki desulfitative cross-coupling reactions with
terminal alkynes and aryl halides, utilizing catalytic pal- sulfonyl chlorides. We report here that arenesulfonyl
ladium, a copper co-catalyst and a base. The process chlorides can be cross-coupled with terminal aryl- and
has been applied to produce antimycotics, antibiot- alkylacetylenes with desulfitation in the presence of pal-
ics, liquid crystals, polymers, and optical or electronic ladium and copper catalysts (Scheme 1).
[
3]
[
4]
[5]
[6]
materials. Aryl bromides and aryl iodides are used nor-
[
7]
mally as arylation agents. Unactivated alkyl bromides
can also undergo cross-couplings with alkynes provided
that N-heterocyclic carbenes are used as ligands for the
palladium. Several groups have developed efficient
procedures for the Sonogashira reaction.
[8]
[
9,10]
Scheme 1.
The most widely employed co-catalysts are copper
salts. Unfortunately, they have the disadvantage to in-
[
11]
duce Glaser-type homocouplings of the alkynes. Tak- Results and Discussion
ing this into account, Sonogashira reactions that do not
[
12]
utilize co-catalysts have also been explored. Practical Our initial exploratory studies engaged para-toluene-
procedures have been proposed by Herrmann and co- sulfonyl chloride (TsCl) and phenylacetylene. With
[13]
[14]
workers, as well as Merck researchers. They utilize 5 mol % of PdCl (PhCN) , 5 mol % CuI as co-catalyst
2
2
palladium complexes with electron-rich ligands such as and bases such as Et N and K CO (Table 1, entries 1
3
2
3
P(t-Bu) , and a base. Very recently, Gelman and Buch- and 2), low yields (¼10%) of the product of desulfita-
3
wald showed that the use of copper co-catalyst inhibits tive cross-coupling were obtained. Under these condi-
[
11]
the reaction between aryl chlorides and tosylates with tions, the major product was diphenylbuta-1,3-diyne
[15]
terminal alkynes. Arene- and alkanesulfonyl chlor- resulting from the oxidative homocoupling of phenyl-
ides are readily available compounds, but have rarely acetylene (Scheme 2).
been used as coupling partners in transition metal-cata-
Adding P(t-Bu) as co-ligand led to an increase of
3
lyzed cross-coupling reactions with organometallic spe- the formation of the desired product of cross-coupling
[
10a]
cies to construct carbon-carbon bonds. Arenesulfonyl (entries 3 and 4). Recently it was reported
that
Adv. Synth. Catal. 2004, 346, 1793–1797
DOI: 10.1002/adsc.200404146
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1793

FULL PAPERS
Srinivas Reddy Dubbaka, Pierre Vogel
and the amount of co-catalyst CuI (entries 10 and 11,
19–21) and found that CuI is necessary for the cross-
coupling and that K CO is a better base than Et N as
2
3
3
it improves the competition between the desired cross-
coupling and undesired homocoupling reactions. We
have also explored the role of diaminocarbene ligands
generated by a-elimination from salts 5–7 (Scheme 3).
Scheme 2.
Na PdCl and P(t-Bu) generate a good catalyst for the But, as seen from Table 1 (entries 22–24), this led to
2
4
3
Sonogashira cross-coupling of aryl chlorides and termi- no cross-coupling at all! With phosphines other than
nal alkynes. In our case (entries 5 and 6) the yield of 1-(4- P(t-Bu) , the yield of product of cross-coupling re-
3
methylphenyl)-2-phenylacetylene never surpassed mained very poor (entries 9, 25–27). We have also ex-
1
1%. Exchanging Na PdCl for Pd(OAc) led to worse amined the role of the solvent and have found that
2 4 2
results (entry 7). In the presence of [(p-allyl)PdCl]2 THFis far better than toluene and acetonitrile.
and P(t-Bu)3 (4:15 mol %) cross-coupling occurred The best conditions found for the desulfitative cross-
with a yield of 30%, together with a 59% yield of the coupling of TsCl and phenylacetylene were then applied
product of homocoupling of phenylacetylene (entry 8). to other substrates (Table 2) including sulfonyl chlorides
Similar results were obtained with Pd (dba) /P(t-Bu)
(
with electron-rich or electron-poor aromatic systems,
entries 10–12, 20 and 21). As the later system is less ex- and various terminal alkynes. As expected, yields of
pensive than [(p-allyl)PdCl] /P(t-Bu) we continued our cross-coupling products 3 increased when using an ex-
2
3
3
2
3
exploration with it. We varied the base (entries 11–18) cess of alkynes 2, as it compensates for the competitive
[a]
Table 1. Screening for Pd-catalyst, co-ligands and bases.
Entry
Catalyst (mol %)
Co-ligand (mol %)
Base
CuI (mol %)
Yield [%] of
[
b]
3
4
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
PdCl (PhCN) (5)
–
–
Et N
5
5
5
ca.10
<6
25
28
<5
11
8
30
<9
25
28
30
9
<8
4
6
10
<10
3
29
30
0
78
2
2
3
PdCl (PhCN) (5)
K CO
62
62
60
30[
13
25
59
43
68
35
50
22
34
45
24
60
50
60[
60
2
2
2
3
3
PdCl (PhCN) (5)
P(t-Bu) (10)
P(t-Bu) (10)
P(t-Bu) (15)
P(t-Bu) (15)
P(t-Bu) (15)
P(t-Bu) (15)
PPh (10)
P(t-Bu) (10)
P(t-Bu) (10)
P(t-Bu) (10)
P(t-Bu) (10)
P(t-Bu) (10)
P(t-Bu) (10)
P(t-Bu) (10)
P(t-Bu) (10)
P(t-Bu) (10)
P(t-Bu) (10)
P(t-Bu) (10)
P(t-Bu) (10)
5 (10)
6 (10)
7 (10)
8 (10)
9 (10)
10 (10)
Et N
2
2
3
3
PdCl (PhCN) (5)
K CO
5
2
2
3
2
Na PdCl (7)
Et N
10
10
10
10
5
2
4
3
3
c]
Na PdCl (7)
Et N
2
4
3
3
Pd(OAc) (7)
Et N
2
3
3
[(p-allyl)PdCl] (4)
Et N
2
3
3
Pd dba (3)
Et N
2
3
3
3
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
Pd dba (3)
Et N
10
5
2
3
3
3
Pd dba (3)
K CO
2
3
3
2
3
3
Pd dba (3)
K CO
10
10
10
10
10
10
10
–
15
15
10
10
10
10
10
10
2
3
3
2
Pd dba (3)
Na CO
2
3
3
2
3
Pd dba (3)
Li CO
2
3
3
2
3
Pd dba (3)
DABCO
DBU
2
3
3
Pd dba (3)
2
3
3
Pd dba (3)
EtN(i-Pr)
2
3
3
2
[d]
Pd dba (3)
-
2
3
3
Pd dba (3)
Et N
2
3
3
3
e]
Pd dba (3)
Et N
2
3
3
3
e
Pd dba (3)
K CO
45
2
3
3
2
3
[(p-allyl)PdCl] (3)
Et N
<40
<16
<2
40
40
27
2
3
Pd dba (3)
K CO
0
0
<13
<10
<15
2
3
2
3
3
Pd dba (3)
K CO
2
3
2
Pd dba (3)
Et N
2
3
3
Pd dba (3)
Et N
2
3
3
Pd dba (3)
Et N
3
2
3
[
a]
All experiments in boiling THF(unless noted), 0.15–0.2 molar, 1: 1.3 mixtures of TsCl and PhC ꢀCH, 5–20 h (until disap-
pearance of TsCl by TLC, yields of 3 based on TsCl after flash chromatography on silica gel.
b]
[
[
[
[
Yields based on phenylacetylene.
In toluene.
N-Methylmorpholine.
Same reaction but in MeCN at 658C, 10 h, the yield in 3 was <5% (ca. 70% 4).
c]
d]
e]
1794
ꢀ 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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Adv. Synth. Catal. 2004, 346, 1793–1797

Pd-Catalyzed Desulfitative Sonogashira–Hagihara Cross-Couplings
FULL PAPERS
Scheme 3. Co-ligand precursors and co-ligands.
[
22]
homocoupling reactions. Recently Ho et al.
found
that homocoupling of alkynes can be retarded under ar- Figure 1. Probable catalytic cycle for the desulfitative Sono-
gashira–Hagihara cross-coupling of arenesulfonyl chlorides
and terminal alkynes.
gon atmosphere diluted with H . In our case (Table 2,
2
entry 1) a 1:1 mixture of Ar/H led to slightly better re-
2
sults. Phase-transfer catalysts such as Bu NBr or Bu NCl
4
4
did not improve the yields in products 3. This contrasts the usual Sonogashira–Hagihara reaction, with the alky-
[
16,21,23]
with several reports
stating that these ammonium nylcopper intermediate (CuCꢀCR); then reductive elim-
(
0)
salts can induce better yield in Heck-type reactions. In ination produces ArCꢀCR and the initial catalyst L Pd
2
one case (Table 2, entry 6) 40 mol % of MeN(oct) Cl (Figure 1). An alternative mechanism is to invoke an ox-
3
led to a lower yield of product of cross-coupling than idative additionof the latter catalystinto the CÀS bond of
in the absence of the phase-transfer catalyst.
the ArSO Cl reagent, followed by desulfitation.
2
At least two possible mechanisms can be operative for
our desulfitative Sonogashira–Hagihara cross-coupling
(
0)
reactions. In one of them, the palladium catalyst L Pd
Conclusion
2
undergoes oxidative addition into the SÀCl bond of the
arenesulfonyl chloride. A fast desulfitation occurs with Arenesulfonyl chlorides undergo desulfitative Stille,
the formation of an ArPdL Cl species that reacts, as in carbonylative Stille, Suzuki–Miyaura and Heck–Mizor-
2
Table 2. Sonogashira–Hagihara desulfitative cross-coupling of arenesulfonyl chlorides 1 and terminal alkynes 2 by using Pd
2
[a]
dba /P(t-Bu) /CuI.
3
3
Entry
Ar in ArSO Cl (1)
R in HCꢀCR (2)
Yield [%] in ArCꢀCR (3) based on 1 using
2
[
b]
[c]
1
.3 equivs. of 2
2 equivs. of 2
[
d]
1
2
3
4
5
6
7
8
9
4-methylphenyl
4-methylphenyl
4-methylphenyl
1-naphthyl
1-naphthyl
1-naphthyl
phenyl
t-butyl
1-hexyl
t-butyl
1-hexyl
1-hexyl
tri(isopropyl)silyl
1-hexyl
tri(isopropyl)silyl
1-hexyl
30 [34]
45
50
40
60
63
65
72
–
60
52
59
52
50
[e]
[f]
55 [52][ [38]
e]
57 [40]
[
g]
[h]
[i]
57 [28] [57]
[d]
1-naphthyl
35 [50][
d]
4-fluorophenyl
4-nitrophenyl
3-cyanophenyl
3-cyanophenyl
40 [43]
41
–
1
1
0
1
t-butyl
–
[
[
[
[
[
[
[
[
[
a]
See details in Experimental Section.
Yields of purified products, after flash chromatography.
Yields were determined through gas chromatography.
b]
c]
d]
e]
f]
1
: 1 Ar/H atmosphere.
2
Et N instead of K CO .
3
2
3
5
4
instead of 15 mol % of CuI.
g]
h]
i]
mol % [(p-allyl)PdCl] and 15 mol % P(t-Bu) instead of the usual conditions.
2
3
With MeN(Oct) Cl (40 mol %).
3
Slow addition of HCꢀCR, 2–4 h.
Adv. Synth. Catal. 2004, 346, 1793–1797
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FULL PAPERS
Srinivas Reddy Dubbaka, Pierre Vogel
oki cross-coupling reactions. We have shown in this pa- molecular mass products). The residue was analyzed by gas
chromatography or/and purified by flash chromatography on
silica gel.
per that they can also be cross-coupled with terminal al-
kynes. The best catalyst found so far for the desulfitative
Sonogashira–Hagihara cross-coupling reactions is
1
-(4-Methylphenyl)-2-phenylacetylene
(Table 2,
en-
[24] 1
try 1):
H NMR (CDCl ): d¼7.44 (d, 2H, J¼8.0 Hz, ArH),
3
Pd (dba) )/P(t-Bu) /CuI using K CO as base, and boil-
2
3
3
2
3
7
(
.41–7.33 (m, 5H, ArH), 7.17 (d, 2H, J¼8.0 Hz, ArH), 2.38
ing THFas medium. Competition of the homocoupling
of the acetylene cannot be avoided, but its effect on the
yields of products of cross-coupling can be reduced by
s, 3H, CH ).
3
1
-(4-Methylphenyl)-2-t-butylacetylene
(Table 2,
en-
[25] 1
try 2):
H NMR (CDCl ): d¼7.24 (d, 2H, J¼7.7 Hz, ArH),
3
slow addition of 2 equivalents of the alkyne to the reac- 7.09 (d, 2H, J¼7.7 Hz, ArH), 2.43 (s, 3H, CH ), 1.39 [s, 9H,
3
tion mixture.
C(CH ) ].
3 3
[26]
1
-(4-Methylphenyl)-2-hexylacetylene (Table 2, entry 3):
1
H NMR (CDCl ): d¼7.24 (d, 2H, J¼7.7 Hz, ArH), 7.09 (d,
3
2
2
3
H, J¼7.7 Hz, ArH), 2.60 (t, 2H, J¼7.0 Hz, CH ), 1.74 (m,
2
H, CH ), 1.57 (m, 2H, CH ), 1.4 (m, 4H, 2ꢁCH ), 0.96 (t,
Experimental Section
2
2
2
H, J¼7.0 Hz, CH ).
3
[27]
1
-(t-But-1-yn-1-yl)naphthalene
(Table 2,
entry 4):
1
General Remarks
H NMR (CDCl
): d¼8.35 (d, 1H, J¼8.6 Hz, ArH), 7.85 (d,
3
1
1
8
H, J¼8.0 Hz, ArH), 7.79 (d, 1H, J¼8.0 Hz, ArH), 7.54 (m,
H, ArH), 7.64 (d, 1H, J¼7.4 Hz, ArH), 7.42 (t, 1H, J¼
.0 Hz, ArH), 7.3 (m, 1H, ArH), 1.47 [s, 9H, 7.0, C(CH ) ].
Unless stated otherwise, reactions were conducted in flame-
dried glassware under a vacuum. THFwas distilled before
use from sodium and benzophenone. Catalysts and ligands
were purchased from Strem Chemical, Inc. All commercially
available reagents were used without further purification. Sol-
vents after reactions and extraction were evaporated in a rota-
tory evaporator under vacuum (solvents were removed by
cooling at À208C, in the case of low boiling point or low mo-
lecular mass products). TLC for reaction monitoring was per-
formed on 60 F254 (Merck) with detection by UV light and char-
3
3
[28]
1
-(Oct-1-yn-1-yl)naphthalene
(Table 2,
entry 5):
1
H NMR (CDCl ): d¼8.38 (d, 1H, J¼8.3 Hz, ArH), 7.86 (d,
3
1
1
7
H, J¼7.7 Hz, ArH), 7.80 (d, 1H, J¼8.3 Hz, ArH), 7.65 (d,
H, J¼7.0 Hz, ArH), 7.56 (m, 2H, ArH), 7.42 (t, 1H, J¼
.3 Hz, ArH), 2.60 (t, 2H, J¼7.0 Hz, CH ), 1.74 (m, 2H,
2
CH ), 1.57 (m, 2H, CH ), 1.4 (m, 4H, 2ꢁCH ), 0.96 (t, 3H,
2
2
2
J¼7.0 Hz, CH ).
3
1
-(1-Naphthyl)-2-(triisopropylsilyl)acetylene (Table 2, en-
1
13
ring with KMnO . H and C NMR spectra were recorded by
4
try 7): R : 0.42 (pentane); oil; IR (film): n¼2942, 2890, 2864,
f
using a Bruker DPX-400 or Bruker ARX-400 spectrometer
À1
2
152, 1462, 1392, 1074, 1014, 996, 881, 798, 772, 736 cm
;
at 400 MHz and 100.6 MHz, respectively, and are reported rel-
1
H NMR (CDCl ): d¼8.42 (d, 1H, J¼8.3 Hz, ArH), 7.85 (t,
1
3
ative to Me Si (d¼0.0) or to the solvents residual H-signal
4
2
1
H, J¼8.8 Hz, ArH), 7.75 (d, 1H, J¼7.4 Hz, ArH), 7.61 (t,
H, J¼7.7 Hz, ArH), 7.54 (t, 1H, J¼7.7 Hz, ArH), 7.44 (t,
H, J¼7.7 Hz, ArH), 1.23 [m, 21H, 3ꢁCH(CH ) ];
1
(
CDCl , d ¼7.27). Data for H NMR spectra are reported as
3
H
follows: chemical shift (d ppm), multiplicity, coupling constant
1
1
3
3 2
(
J in hertz) and integration. Data for C NMR spectra report-
13
C NMR: d¼133.5, 133.1, 131.0, 128.8, 128.3, 126.8, 126.4,
ed in terms of chemical shift. IR spectra were recorded on a
Perkin-Elmer 1420 spectrometer and are reported in frequen-
1
3
1
26.3, 125.2, 121.2, 104.9, 95.8, 18.8, 11.4; MS: m/z (rel. int.)¼
þ
08 (M , 43), 265 (67), 237 (17), 223 (43), 209 (58), 195 (100),
À1
cy of absortion (cm ). HRMS (MALDI-TOF) mass spectra
79 (32), 165 (22), 105 (23), 85 (8); HRMS (MALDI-TOF):
were taken on a Kratos Analytical Instruments system.
calcd. for C H Si: 308.1960; found: 308.1967.
2
1
28
1
-(4-Fluorophenyl)-2-hexylacetylene (Table 2, entry 8): Rf:
0
.39 (pentane); oil; IR (film): n¼2955, 2938, 2858, 2352,
À1
1
Typical Experimental Procedure for Desulfitative
Sonogashira–Hagihara Cross-Coupling Reactions
1601, 1507, 1465, 1427, 1230, 835 cm ; H NMR (CDCl ):
3
d¼7.38 (td, 2H, J¼8.6, 3.2 Hz, ArH), 6.99 (t, 2H, J¼8.6 Hz,
(
Table 2)
ArH), 2.40 (t, 2H, J¼7.0 Hz, CH
), 1.53 (m, 2H, CH ), 1.40
2 2
(
m, 2H, CH ), 1.3 (m, 4H, 2ꢁCH ), 0.91 (t, 3H, J¼7.0 Hz,
2
2
A round-bottom flask was dried under vacuum, and to the flask
were added the corresponding arenesulfonyl chloride
13
CH ); C NMR: d¼162.4, 133.7, 117.8, 115.7, 90.5, 79.8, 31.7,
3
þ
2
1
(
2
8.9, 28.7, 22.9, 19.6, 14.4; MS: m/z (rel. int.)¼204 (M , 5),
(
1.00 mmol), Pd dba (0.03 mmol), CuI (0.15 mmol) and also
2 3
89 (11), 147 (16), 133 (37), 119 (24), 105 (51), 91 (100), 79
an internal standard (4,4’-dimethyldiphenyl, 0.25 mmol) under
a nitrogen atmosphere (glove-box). The flask was connected to
a vacuum line and filled with Ar (three times), then THF
þ
84); HRMS (MALDI-TOF): calcd. for [C H FþK] :
1
4
17
43.0951; found: 243.0959.
-(4-Nitrophenyl)-2-(triisopropylsilyl)acetylene (Table 2,
1
(
4 mL) was added under Ar. Next, P(t-Bu) [0.1 mmol, P(t-
[29] 1
3
entry 9):
H NMR (CDCl ): d¼8.20 (d, 2H, J¼8.9 Hz,
3
Bu) sold by Strem Chemicals in a Sure/Seal bottle as a
3
ArH), 7.63 (d, 2H, J¼8.9 Hz, ArH), 1.15–1.13 [m, 21H, 3ꢁ
1
0 wt % solution in hexane], K CO (2.5 mmol) or Et N
2
3
3
CH(CH ) ].
3
2
(
2.5 mmol, in 1 mL of THF), were added in that order. The al-
kyne (1.3 to 2.0 mmol) was added via a syringe under reflux and
the mixture stirred for 5–10 h. After cooling to 208C, the mix-
ture was diluted with Et O and washed with H O. The aqueous Acknowledgements
2
2
layer was extracted again with Et O (3 times). The combined
2
organic phases were dried (MgSO ), filtered, and concentrated
under reduced pressure (solvents were removed under reflux
and cooling to À208C in the case of low boiling point or low
We thank the Swiss National Science Foundation (Grant No.
2000–2100002/1) and the Office Federal de Education et de la
Sciences, (Grant No. COI. 0071, COST D13/010/01). We thank
4
1796
ꢀ 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
asc.wiley-vch.de
Adv. Synth. Catal. 2004, 346, 1793–1797

Pd-Catalyzed Desulfitative Sonogashira–Hagihara Cross-Couplings
FULL PAPERS
also Mr. M. Rey, F. Sep u´ lveda and Dr. A. Rezaname for techni-
cal help.
[10] a) A. Kçllhofer, T. Pullmann, H. Plenio, Angew. Chem.
2003, 115, 1086; Angew. Chem. Int. Ed. 2003, 42, 1056;
b) M. Ansorge, T. J. J. Müller, J. Organomet. Chem.
1
999, 585, 174; c) Y. Nishihara, K. Ikegashira, K. Hira-
bayashi, J. Ando, A. Mori, T. Hiyama, J. Org. Chem.
000, 65, 1780; d) M. R. Buchmeiser, T. Schareina, R.
References and Notes
2
[
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