Palladium-catalyzed arylation of sulfones

Article abstract of DOI:10.1023/B:RUJO.0000044542.70121.04

A procedure was developed for monoarylation of sulfones with aryl halides in the presence of palladium complexes. Optimal reaction conditions were found, and the scope of application of the proposed procedure was determined. The arylation occurs only with those sulfones which are relatively strong CH acids; the corresponding monoarylated sulfones are formed in moderate to high yields. The arylation of carbanions derived from the sulfones and some other CH acids requires the presence of an additional equivalent of base. The presence of the latter is also necessary in stoichiometric reactions of carbanions with the palladium complex CF3C6H4Pd(PPh3)2Br; no reaction occurs in the absence of a base. A new mechanism of arylation was proposed, where the key stage is deprotonation of palladium intermediate ArPdL2CHXY which activates the reductive elimination stage.

Full text of DOI:10.1023/B:RUJO.0000044542.70121.04

Russian Journal of Organic Chemistry, Vol. 40, No. 6, 2004, pp. 802–812. Translated from Zhurnal Organicheskoi Khimii, Vol. 40, No. 6, 2004,
pp. 841–853.
Original Russian Text Copyright © 2004 by Mitin, Kashin, Beletskaya.
Dedicated to Full Member of the Russian Academy of Sciences
O.N. Chupakhin on his 70th Anniversary
Palladium-Catalyzed Arylation of Sulfones
A. V. Mitin, A. N. Kashin, and I. P. Beletskaya
Faculty of Chemistry, Lomonosov Moscow State University, Vorob’evy gory 1, Moscow, 119992 Russia
e-mail: beletska@org.chem.msu.ru
Received February 22, 2004
Abstract—A procedure was developed for monoarylation of sulfones with aryl halides in the presence of
palladium complexes. Optimal reaction conditions were found, and the scope of application of the proposed
procedure was determined. The arylation occurs only with those sulfones which are relatively strong CH acids;
the corresponding monoarylated sulfones are formed in moderate to high yields. The arylation of carbanions
derived from the sulfones and some other CH acids requires the presence of an additional equivalent of base.
The presence of the latter is also necessary in stoichiometric reactions of carbanions with the palladium
complex CF3C6H4Pd(PPh3)2Br; no reaction occurs in the absence of a base. A new mechanism of arylation was
proposed, where the key stage is deprotonation of palladium intermediate ArPdL2CHXY which activates the
reductive elimination stage.
Sulfones constitute an important class of organic
synthons which are used for the preparation of
a number of natural and biologically active compounds
[1–3]. Wide application of sulfones in organic syn-
thesis results from important properties of the sulfonyl
group: being a strong electron acceptor, it facilitates
deprotonation of the neighboring carbon atom thus
favoring various transformations of the resulting
stabilized carbanions; on the other hand, this group can
readily be removed by reductive desulfonylation under
mild conditions (Scheme 1).
The arylation of carbanions with aryl halides in the
presence of palladium complexes is now the subject of
extensive studies [5, 6]. In most cases, the arylation of
such CH acids as ketones, amides, diethyl malonate,
cyclic diketones, nitroalkanes, amides, esters, and
protected amino acids can be achieved with the use of
electron-donor and sterically hindered phosphine or
carbene ligands [7]. Simple ligands like triphenyl-
phosphine are efficient in the monoarylation of α-func-
tionalized nitriles YCH2CN [8]. On the whole, it still
remains unclear how the nature of CH acid determines
the possibility for its arylation.
Scheme 1.
Scheme 2.
B–
CHSO2R
CSO2R
SO2R
Base, [Pd]/L
–BH
SO2R
Ar(Ht)X
+
YCH2SO2R
Ar(Ht) CH
E+
[H]
Y
C
CH E
Y is an electron-acceptor group.
E
Alkyl-substituted sulfones are often synthesized
following the known scheme where the key stage is
alkylation of the corresponding carbanions. However,
in most cases this scheme cannot be applied to intro-
duction of an aryl or vinyl group. For this purpose, we
proposed a procedure based on direct arylation with
aryl halides under catalysis by palladium complexes
[4] (Scheme 2).
In the present work we examined arylation of
various sulfones (Tables 1–4) with aryl halides with
the goal of determining the applicability limits of the
above procedure, specifically those originating from
CH acidity of the substrate. Also, the effect of the
sulfone structure and reaction conditions on the
product yield was considered. The results allowed us
to propose a new mechanism of arylation of CH acids.
1070-4280/04/4006-0802 © 2004 MAIK “Nauka/Interperiodica”

PALLADIUM-CATALYZED ARYLATION OF SULFONES
803
Table 1. Reactions of PhSO2CH2CO2Et and C6F5CH2SO2CF3 with 4-bromobenzotrifluoridea
Run
no.
Conversion
of ArBr, %
Yield,c
%
Base (solvent)
Ligandb
Catalyst
PhSO2CH2CO2Et
Time, h
d
01
02
03
04
05
06
07
08
09
10
11
12
13
Cs2CO3 (dioxane)
K3PO4 (dioxane)
t-BuOK (toluol)
t-BuOK (dioxane)
t-BuOK (dioxane)
t-BuOK (dioxane)
t-BuOK (dioxane)
NaHMDS (dioxane)e
NaH (dioxane)
BINAP
BINAP
BINAP
BINAP
DPPF
Xanthphos
PPh3
Pd2dba3·CHCl3
Pd2dba3·CHCl3
Pd2dba3·CHCl3
Pd2dba3·CHCl3
Pd2dba3·CHCl3
Pd2dba3·CHCl3
Pd2dba3·CHCl3
Pd2dba3·CHCl3
Pd2dba3·CHCl3
Pd2dba3·CHCl3
3
120
3
000
034
053
100
100
100
100
100
100
100
100
008
031
–
–
32
53
52
54
57
70
82
77
80
–
3
3
3
3
PPh3
3
PPh3
3
NaH (dioxane)
DPPF
PPh3
3
NaH (dioxane)
4-CF3C6H4Pd(PPh3)2Br
PdCl2
3
NaH (dioxane)
PPh3
3
f
NaH (dioxane)
PPh3
[Pd(dmba)Cl]2
3
17
C6F5CH2SO2CF3
Pd2dba3·CHCl3
Pd2dba3·CHCl3
Pd2dba3·CHCl3
Pd2dba3·CHCl3
Pd2dba3·CHCl3
Pd2dba3·CHCl3
14
15
16
17
18
19
NaH (DME)
NaH (DME)
NaH (DME)
NaH (DME)
NaH (DME)
NaH (DME)
Ph3As
PFu3
5
5
5
5
5
5
066
065
063
051
075
013
55
54
51
40
37
08
PPh3
DBPBP
P(t-Bu)3
DPPBz
a
The reaction was carried out at 70°C using 4 mol % of the palladium catalyst (2 mol % of Pd2dba3 ·CHCl3), ratio Pd/(L~L) =
1/1.5, Pd/L = 1/3; amounts of the reactants: CH acid, 0.16 mol; 4-bromobenzotrifluoride, 0.125 mmol; base, 0.375 mmol; solvent, 4 ml.
DPPF is 1,1'-bis(diphenylphosphino)ferrocene, Xantphos is 9,9-dimethyl-4,5-bis(diphenylphosphino)xanthene, DBPBP is 2-(diphenyl-
phosphino)biphenyl, and DPPBz is 1,2-bis(diphenylphosphino)benzene.
b
c
d
e
f
According to the GLC data.
dba is dibenzylideneacetone.
HMDSH is hexamethyldisilazane.
dmba is cyclometalated dimethylbenzylamine.
The conditions of arylation with 4-bromobenzo-
disilazide, and potassium tert-butoxide. The latter
promotes a side reaction leading to formation of the
corresponding biaryl; as a result, the yield of the target
product appreciably decreases (Table 1, run no. 7). The
maximal yields were achieved with the use of sodium
hydride (Table 1, run no. 9). The ligand nature was
found to only slightly affect the process: the yield
varied in the range from 37 to 55% in the series of
ligands differing in their donor properties (Table 1, run
nos. 14–18). Likewise, no appreciable difference was
observed in the efficiency of bi- and unidentate
ligands. An exception was bidentate 1,2-bis(diphenyl-
phosphino)benzene (DPPBz) which is characterized by
trifluoride were optimized using ethyl phenylsulfonyl-
acetate and pentafluorobenzyl trifluoromethyl sulfone
as model substrates (Table 1). The reaction occurs in
ethers such as dioxane and 1,2-dimethoxyethane. In
weakly polar toluene, the reaction was slow, presum-
ably because of poor solubility of the corresponding
CH acid salt (Table 1, run no. 3). Among the examined
catalytic precursors, the most effective were
Pd2dba3 ·CHCl3 and 4-CF3C6H4Pd(PPh3)2Br. Weak
bases like Cs2CO3 and K3PO4 turned out to be inef-
fective, and the reaction occurred only in the presence
of strong bases: sodium hydride, sodium hexamethyl-
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

MITIN et al.
804
Table 2. Palladium-catalyzed arylation of sulfones with 4-bromobenzotrifluoridea
Run
no.
Time,
h
Conversion
of ArBr, %
b
pKa
Product
Yield,c %
CH acid
01
5
012
013
100
100
100
–
d00d
00
PhSO2Me
29.0
–
–
02 PhSO2CH2C6F5
03 PhSO2CH2CO2Et
04 PhSO2CH2SO2CH3
05 PhSO2CH2SO2Ph
06 PhSO2CH2CN
–
–
–
5
3
4-F3CC6H4CH(SO2Ph)CO2Et
4-F3CC6H4CH(SO2Ph)SO2Me
83
3
82
12.2 4-F3CC6H4CH(SO2Ph) 2
12.0 PhCH(SO2Ph)CN
3
85
e82e
–
07 PhSO2CH2COPh
08 PhSO2CH2NO2
11.4 4-F3CC6H4CH(SO2Ph)COPh
0.4.5
0.4.5
100
100
30
07.1
72
4-F3CC6H4CH(SO2Ph)NO2
09 PhCH2CH2SO2CH2CO2Et
10 cyclo-C6H13SO2CH2CO2Et
11 4-F3CC6H4CH(SO2Ph)CO2Et
12 PhSO2CH(Me)CO2Et
–
–
–
–
4-F3CC6H4CH(CO2Et)SO2CH2CH2Ph
8
8
8
8
100
100
018
017
75
66
00
00
4-F3CC6H4CH(CO2Et)SO2C6H13-cyclo
–
–
a
The reactions were carried out using 0.5 mmol of aryl halide, 0.65 mmol of CH acid, 2 mol % of Pd2dba3 ·CHCl3 (4 mol % of Pd),
12 mol % of PPh3, 1.5 mmol of NaH, and 4 ml of DME at 70°C under argon.
b
c
d
e
pKa in DMSO[10].
Yield of the isolated product (by column chromatography).
No reaction occurred in the presence of BuLi as base.
In the reaction with bromobenzene [7].
a small bite angle; the use of that ligand afforded
a strongly reduced yield (Table 1, run no. 19). There-
fore, accessible and inexpensive triphenylphosphine
was used in most experiments.
4-bromobenzotrifluoride with a series of substituted
sulfones whose CH acidity varies over a wide pKa
range [10].
The data in Table 2 show that the arylation readily
occurs with sulfones having an additional functional
group in the α-position, which are relatively strong CH
acids (Table 2, run nos. 3–9). Even such a strong
CH acid (pKa = 7.1) as nitromethyl phenyl sulfone
undergoes arylation (Table 2, run no. 8). In these
reactions, the corresponding monoarylation products
It is known that the reactivity of carbanions in the
alkylation processes correlates with pKa values of the
conjugate CH acids: stronger CH acids produce less
nucleophilic carbanions [9]. In order to estimate the
relation between the reactivity of sulfones toward
arylation and their structure we examined reactions of
Table 3. Palladium-catalyzed arylation of some trifluoromethyl sulfones with aryl halidesa
Conversion
of ArBr, %
Run no.
Trifluoromethyl sulfone
Aryl halide
Time, h
Yield,b %
1
2
3
4
5
6
7
CF3SO2Ph
4-CF3C6H4Br
4-CF3C6H4Br
4-CF3C6H4Br
4-CF3C6H4Br
4-ClC6H4Br
20
40
14
12
24
24
24
79
57
51
94
71
31
20
67
36
30
81
48
–
CF3SO2C6H4Br-4
CF3SO2C6H4Br-3
CF3SO2C6F5
CF3SO2C6F5
CF3SO2CH2CH2Ph
CF3SO2CH2COOEt
4-CF3C6H4Br
4-CF3C6H4Br
–
a
The reactions were carried out using 0.5 mmol of aryl halide, 0.65 mmol of CH acid, 2 mol % of Pd2dba3 ·CHCl3 (4 mol % of Pd),
12 mol % of PPh3, 1.5 mmol of NaH, and 4 ml of DME at 70°C under argon.
b
Yield of the isolated product (by column chromatography).
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PALLADIUM-CATALYZED ARYLATION OF SULFONES
805
Table 4. Palladium-catalyzed arylation of ethyl phenylsulfonylacetate and bis(phenylsulfonyl)methanea
Run
no.
Time,
h
Conversion
of ArBr, %
Yield,b %
Aryl halide
Product
PhSO2CH2CO2Et
01
02
03
04
05
06
07
08
PhBr
09
08
03
04
27
20
03
12
PhCH(SO2Ph)CO2Et
100
091
100
100
075
100
100
085
72
74
83
64
25
41
71
62
4-MeC6H4Br
4-MeC6H4CH(SO2Ph)CO2Et
4-F3CC6H4CH(SO2Ph)CO2Et
3-FC6H4CH(SO2Ph)CO2Et
4-F3CC6H4CH(SO2Ph)CO2Et
4-MeOC6H4CH(SO2Ph)CO2Et
4-MeOC6H4CH(SO2Ph)CO2Et
1-C10H7CH(SO2Ph)CO2Et
(PhSO2)2CH2
4-F3CC6H4Br
3-FC6H4Br
4-F3CC6H4Cl
4-MeOC6H4Br
4-MeOC6H4I
1-Bromonaphthalene
09
10
11
4-F3CC6H4Br
03
04
06
4-F3CC6H4CH(SO2Ph)2
3-FC6H4CH(SO2Ph)2
100
100
100
85
81
77
3-FC6H4Br
1-Bromonaphthalene
1-C10H7CH(SO2Ph)2
a
The reactions were carried out using 0.5 mmol of aryl halide, 0.63 mmol of CH acid, 1.4 mmol of NaH, 2 mol % of Pd2dba3 ·CHCl3,
12 mol % of PPh3, and 4 ml of DME at 70°C under argon.
b
Yield of the isolated product (by column chromatography).
Table 5. Palladium-catalyzed arylation of ethyl phenylsulfonylacetate and bis(phenylsulfonyl)methane with hetaryl bromides
ans trans-β-bromostyrenea
Time, h
Conversion, %
Yield,b %
Run no.
Aryl halide
Product
PhSO2CH2CO2Et
1
2
3-Bromopyridine
6
6
3-C5H4NCH(SO2Ph)CO2Et
trans-PhCH=CHCH(SO2Ph)CO2Et
(PhSO2)2CH2
094
100
51
40
trans-BrCH=CHPh
3
4
5
3-Bromothiophene
3-Bromopyridine
3-Bromoquinoline
8
5
6
3-C4H3SCH(SO2Ph)2
100
097
100
77
90
76
3-C5H4NCH(SO2Ph)2
3-C9H6NCH(SO2Ph)2
a
The reactions were carried out using 0.5 mmol of aryl halide, 0.63 mmol of CH acid, 1.4 mmol of NaH, 2 mol % of Pd2dba3 ·CHCl3,
12 mol % of PPh3, and 4 ml of DME at 70°C under argon.
b
Yield of the isolated product (by column chromatography).
Weak CH acids were completely inert in the
arylation under the given conditions. We did not
succeed in effecting the arylation of methyl phenyl
sulfone even when butyllithium was used as a base,
though the latter is known to quantitatively depro-
tonate the substrate (Table 2, run no. 1). Sulfones with
a tertiary α-carbon atom also failed to react (Table 2,
run nos. 9, 10). Obviously, the same factor is respons-
ible for the observed selectivity; i.e., only one aryl
group is introduced.
are formed mainly in high yields (72–85%). An excep-
tion is phenacyl phenyl sulfone (Table 2, run no. 7), for
its sodium salt is poorly soluble; the yield of the
arylation product is only 30%. Trifluoromethylsulfonyl
group exerts a strong activating effect: substituted
benzyl trifluoromethyl sulfones turned out to be
reactive (Table 3), while analogous compounds with
a phenylsulfonyl group failed to react (Table 2, run
no. 2). It should be noted that, among the examined
benzyl trifluoromethyl sulfones, the reaction occurred
most readily with the sulfone containing an electron-
acceptor perfluorophenyl group (Table 3, run no. 4).
Unfortunately, the arylation of some sulfones was
unsuccessful because of decomposition of the initial
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

MITIN et al.
806
compound. For example, PhSO2CH2SiMe3 underwent
desilylation to methyl phenyl sulfone instead of
arylation. Ethyl pentafluorobenzylsulfonylacetate and
ethyl benzylsulfonylacetate decomposed to give salts
of the corresponding sulfinic acid, C6F5CH2SO2H and
PhCH2SO2H. The same products were obtained by the
action of NaH or t-BuOK in the absence of a catalyst.
a half of the initial carbanion would be consumed for
deprotonation of the product which is a stronger CH
acid than the initial sulfone. However, sodium hydride
promotes side reduction of the aryl halide to the
corresponding arene, so that the yield of the major
product decreases [11] (Scheme 3).
In order to avoid the reduction of aryl halide with
sodium hydride we used two-fold amount of initial CH
acid. Contrary to expectations, no reaction occurred at
all. Analogous pattern was also observed in reactions
with other CH acids, such as ethyl cyanoacetate and
malonodinitrile. As follows from the data in Table 6,
apart from carbanion, the presence of an additional
amount of a strong base (NaH, t-BuOK, or NaHMDS)
is necessary for the reaction to proceed. These results
cannot be interpreted in terms of the known mecha-
nism of cross-coupling with participation of carbanions
(Scheme 4).
Under the optimal conditions we performed reac-
tions of the most active CH acids, ethyl phenyl-
sulfonylacetate and bis(phenylsulfonyl)methane with
various aryl halides (Table 4) and hetaryl halides
(Table 5). The reactions readily occurred with aryl
bromides and aryl iodides, the latter being more reac-
tive (Table 4, run nos. 6, 7). As a result, the corre-
sponding monoarylation products were obtained in
moderate to high yields.
Aryl chlorides are difficult to react with sulfones.
Even with activated 4-chlorobenzotrifluoride, the reac-
tion stops while the conversion is not complete, and
the product yield is poor. Analogous results were
obtained with the use of electron-donating sterically
hindered phosphines [PCy3 and 2,2'-bis(tert-butylphos-
phino)biphenyl] as ligands, though the same ligands
were effective in other reactions of carbanions with
aryl chlorides [5, 6].
Scheme 4.
ArBr
Pd(0)L2
ArPdL2Br
[CHXY]_
trans-β-Bromostyrene also reacted with ethyl
phenylsulfonylacetate (Table 5, run no. 2) to give the
corresponding vinylation product without change of
the position and configuration of the double bond. This
reaction is the first example of palladium-catalyzed
vinylation of CH acids.
Br _
ArCHXY
B– –BH
[ArCXY]_
ArPdL2CHXY
In all the above reactions, no less than 2 equiv of
a base should be used, for it is consumed for metala-
tion of not only the initial CH acid but also the
arylation product. Otherwise, i.e., with an equimolar
amount of base, the conversion would not exceed 50%:
The role of base in the arylation of carbanions was
studied by reacting carbanions derived from sulfones
with a stoichiometric amount of the preliminarily
prepared palladium complex 4-CF3C6H4Pd(PPh3)2Br in
the presence of a base and without it. These reactions
simulate the stages of bromine replacement and reduc-
tive elimination in the catalytic series. Preliminarily
prepared ethyl phenylsulfonylacetate sodium salt did
not react with the complex 4-CF3C6H4Pd(PPh3)2Br in
the absence of a base on heating in dioxane or tetra-
Scheme 3.
Br
1
hydrofuran for 12 h at 70°C. The H and 19F NMR
+
YCH2SO2Ph
SO2Ph
spectra of the reaction mixture contained signals only
from the initial compounds, and addition of hexane to
the mixture resulted in precipitation of unchanged
4-CF3C6H4Pd(PPh3)2Br. After addition of NaHMDS or
NaH, in 3 h at 70°C the corresponding monoarylation
product was obtained in 65 and 33% yield, respec-
tively. In the latter case, the arylation was accompanied
by reduction of the complex to the free arene (yield
Y
NaH, DME
Pd2dba3/PPh3
+
Y = SO2Ph
Y = CO2Et
77%
62%
05%
18%
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

PALLADIUM-CATALYZED ARYLATION OF SULFONES
807
Scheme 5.
Dioxane or THF-d8
70°C
–
F3C
Pd(PPh3)2Br
+
EtOCO CH SO2Ph Na+
Dioxane, NaH
70°C
CO2Et
SO2Ph
–
F3C
Pd(PPh3)2Br
+
EtOCO CH SO2Ph Na+
F3C
Na+
+
PhCF3
33%
46%
Dioxane, NaHMDS
70°C
CO2Et
SO2Ph
–
F3C
Pd(PPh3)2Br
+
EtOCO CH SO2Ph Na+
F3C
Na+
65%
THF, 80°C
–
F3C
Pd(PPh3)2Br
+
CF3SO2 CH C6F5
Na+
C6F5
THF, NaH, 80°C
–
F3C
Pd(PPh3)2Br
+
CF3SO2 CH C6F5
Na+
F3C
Na+
SO2CF3
48%
45%). Analogous effect of a base was observed in the
arylation of carbanion derived from pentafluorobenzyl
trifluoromethyl sulfone C6F5CH2SO2CF3. In the pres-
ence of sodium hydride, the carbanion reacted with
4-CF3C6H4Pd(PPh3)2Br to afford 48% of the mono-
arylation product (according to the GLC data), while
no such product was formed in the absence of a base
(Scheme 5).
the rate-determining stage in the arylation process is
reductive elimination which is hindered for the neutral
complex ArPdL2CHXY formed from carbanion.
Deprotonation of ArPdL2CHXY by the action of
a strong base gives anionic palladium complex
[ArPdL2CXY]– which then undergoes reductive
elimination. Scheme 6 illustrates the catalytic series
involving the above deprotonation stage.
Thus the role of a base in the catalytic and
stoichiometric arylation of carbanions is the same: the
reaction occurs only in the presence of excess basic
reagent. This may be explained on the assumption that
It remains unclear why the bromine atom in the
complex ArPdL2Br cannot be replaced by carbanion in
a stoichiometric reaction. Presumably, the stage of
halogen substitution in the palladium complex by
a strongly stabilized carbanion is reversible and the
equilibrium is displaced toward the initial carbanion.
Therefore, only the subsequent reductive elimination
shifts the equilibrium. The assumption that deprotona-
tion of ArPdL2CHXY precedes the reductive elimina-
tion stage is consistent with the lack of arylation
of sulfonyl CH acids with a tertiary α-carbon atom
[RSO2CH(R')Y]; deprotonation of the corresponding
palladium complex is impossible. For the same reason,
the other sulfones give rise exclusively to monoaryla-
tion products.
Scheme 6.
ArBr
Pd(0)L2
ArPdL2Br
[CHXY] _
Br _
[ArCXY]_
[ArPdL2CXY] _
ArPdL2CHXY
Obviously, the role of a base in the examined
reactions consists in activation of the reductive
elimination from ArPdL2CHXY, and it does not affect
cis–trans isomerization process. The presence of
Base
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

MITIN et al.
Table 6. Effect of base in the palladium-catalyzed arylation of CH acidsa
808
No excess base
Excess base (NaH)
conversion of
Run
no.
CH acid
Reaction conditions
conversion of
time, h
12
time, h
ArBr, % (yield, %)
ArBr, % (yield, %)
b1b
PhSO2CH2CO2Et
Dioxane, 70°C, L = PPh3
0 (0)5 (0)
12
082 (61)
2
3
4
5
6
7
8
PhSO2CH2CO2Et
(PhSO2)2CH2
Dioxane, 70°C, L = DPPF
DME, 70°C, L = PPh3
DME, 70°C, L = PPh3
DME, 70°C, L = PPh3
DME, 70°C, L = PPh3
08
12
12
12
12
04
04
02
13
00
00
00
00
00
04
04
12
15
06
04
04
100 (77)
100 (86)
087 (71)
086 (72)
100 (84)
100 (70)
100 (56)
C6F5CH2SO2CF3
NCCH2COOEt
NCCH2CN
c
PhSO2CH2CO2Et
PhSO2CH2CO2Et
DME, 70°C, L = PPh3
d
DME, 70°C, L = PPh3
a
The reactions were carried out at 70°C in dioxane or DME; amounts of the reactants: 4-bromobenzotrifluoride, 0.5 mmol;
Pd2dba3 ·CHCl3, 2 mol %; L:Pd ratio 3:1; solvent, 4 ml; in the presence of excess base: NaH, 1.25 mmol; CH acid, 0.65 mmol; no excess
base: NaH, 1.0 mmol; CH acid, 1.25 mmol.
b
c
d
1-Bromonaphthalene was used as aryl halide.
Potassium tert-butoxide was used as base.
Sodium hexamethyldisilazide was used as base.
excess basic reagent is also necessary in reactions with
bidentate DPPF, where only the cis-complexes are
involved (Table 6, run no. 2). The proposed arylation
mechanism allows us to explain the unusual relation
between the reactivity of sulfones and their pKa values.
As noted above, relatively weak CH acids, such as
MeSO2Ph, PhCH2SO2Ph, and C6F5CH2SO2Ph, fail to
react; this is not the result of their difficult deprotona-
tion, for the corresponding preliminarily prepared CH
acid salts do not undergo arylation as well. Presum-
ably, intermediate ArPdL2CHXY is a weaker CH acid
than the initial sulfone; therefore, deprotonation of
palladium intermediate is possible only when the
corresponding CH acid is sufficiently strong.
Functionalized sulfones were prepared according to the
procedures reported in [13, 14]. Trifluoromethyl sul-
fones were synthesized from the corresponding alkyl
bromides and potassium trifluoromethanesulfinate
[15]. Bromo(4-trifluoromethylphenyl)bis(triphenyl-
phosphine)palladium(II) was synthesized following the
procedure described in [16].
1
The H, 13C, and 19F NMR spectra were recorded
from solutions in CDCl3 (unless otherwise stated)
1
13
using a Varian VXR-400 spectrometer; the H and C
chemical shifts were measured relative to tetramethyl-
silane as internal reference. The IR spectra were
obtained from samples prepared as KBr pellets. The
mass spectra (electron impact, 70 eV) were run on
Cratos MS-30 and MS-890 instruments. GLC analysis
was performed on a Hewlett– Packard 5890 Series II
Plus chromatograph equipped with a flame-ionization
detector and an HP-1 capillary column (25 m×
0.32 mm, film thickness 0.25 µm); helium was used
as carrier gas.
Finally, the arylation can be completed by reaction
with another electrophilic reagent rather than by
protonation of the carbanion thus formed. To illustrate
this possibility, we performed chlorination and allyla-
tion of aryl methyl sulfones by the action of N-chloro-
succinimide (NCS) and allyl or geranyl acetate,
respectively. The reaction conditions and yields are
given in Table 7.
Arylation of sulfones with aryl halides. A reactor
was charged in a stream of argon with 0.65 mmol of
sulfone, 15.8 mg (12 mol %) of triphenylphosphine,
10.4 mg (2 mol %) of Pd2dba3·CHCl3, 10–20 mg of
naphthalene (internal standard), 60 mg (1.5 mmol) of
sodium hydride (a 60% suspension in oil), and
0.5 mmol of aryl halide. The reactor was cooled with
liquid nitrogen and evacuated, and 4 ml of 1,4-dioxane
was condensed thereto. The mixture was degassed by
EXPERIMENTAL
Dioxane, tetrahydrofuran, and 1,2-dimethoxyethane
were purified and dehydrated by standard procedures.
Dioxane and DME were stored over potassium
diphenylketyl under reduced pressure. The complex
Pd2dba3·CHCl3 was synthesized as described in [12].
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

PALLADIUM-CATALYZED ARYLATION OF SULFONES
Table 7. Arylation of sulfones with subsequent treatment with electrophilea
809
Sulfone
Aryl bromide
Electrophile
Product
Yield,b %
PhCH2CH2SO2CH2CO2Et
PhSO2CH2SO2CH3
4-CF3C6H4Br NCSc
4-CF3C6H4Br NCSc
4-CF3C6H4CCl(CO2Et)SO2CH2CH2Ph
4-CF3C6H4CCl(SO2Me)SO2Ph
72
82
62
68
80
73
cyclo-C6H13SO2CH2CO2Et 4-CF3C6H4Br NCSc
4-CF3C6H4CCl(CO2Et)SO2C6H13-cyclo
3-C5H4NC(SO2Ph)2CH2CH=CH2
(PhSO2)2CH2
3-C5H4NBr
Allyl acetated
PhSO2CH2CO2Et
PhSO2CH2CO2Et
4-CF3C6H4Br Allyl acetated
4-CF3C6H4Br Geranyl acetated
4-CF3C6H4C(CO2Et)(SO2Ph)CH2CH=CH2
4-CF3C6H4C(CO2Et)(SO2Ph)C10H17
a
The reactions were carried out with 0.5 mmol of aryl halide, 0.63 mmol of sulfone, 1.4 mmol of NaH, 2 mol % of Pd2dba3 ·CHCl3,
12 mol % of PPh3, and 4 ml of DME at 70ºC under argon; when the arylation was complete, electrophilic reagent was added.
b
c
d
Yield of the isolated product (by column chromatography).
1 mmol, 20ºC, 12 h.
1 mmol, 40ºC, 12 h.
triple freeze–thaw procedure, and the reactor was filled
with argon. The reaction was carried out by stirring at
70°C, and its progress was monitored by GLC and
TLC (Silufol UV-254). When the reaction was com-
plete, the mixture was diluted with water acidified with
1 drop of concentrated hydrochloric acid and treated
with diethyl ether (3×10 ml). The extract was
evaporated, and the residue was subjected to
chromatographic separation on silica gel (40–100 µm)
using ethyl acetate–petroleum ether (bp 65–68°C) as
eluent.
phenylsulfonylacetate. Yield 118 mg, colorless crys-
tals with mp 104–105°C. IR spectrum, ν, cm–1: 1147,
1
1324 (SO2); 1735 (CO2). H NMR spectrum, δ, ppm:
1.22 t (3H), 2.34 s (3H), 4.1–4.3 m (2H), 5.06 s (1H),
7.10 d (2H), 7.23 d (2H), 7.44 t (2H), 7.59–7.64 m
(3H). Found, %: C 64.06; H 5.71. C17H18O4S. Cal-
culated, %: C 64.15; H 5.66.
Ethyl 3-fluorophenyl(phenylsulfonyl)acetate
PhSO2CH(CO2Et)C6H4F-3 was obtained from 88 mg
of 3-bromofluorobenzene and 148 mg of ethyl phenyl-
sulfonylacetate. Yield 103 mg, colorless crystals,
mp 83–84°C. IR spectrum, ν, cm–1: 1149, 1326 (SO2);
Ethyl phenyl(phenylsulfonyl)acetate PhSO2CH-
(Ph)CO2Et was obtained from 78.5 mg of bromo-
benzene and 148 mg of ethyl phenylsulfonylacetate.
Yield 110 mg, colorless crystals with mp 95–97°C. IR
spectrum, ν, cm–1: 1149, 1322 (SO2); 1737 (CO2).
1H NMR spectrum, δ, ppm: 1.237 t (3H), 4.14–4.29 m,
(2H), 5.095 s (1H), 7.29 t (2H), 7.33–7.40 m (3H),
7.43 t (2H), 7.58–7.64 m (3H). Found, %: C 63.47;
H 5.11. C16H16O4S. Calculated, %: C 63.14; H 5.30.
1
1735 (CO2). H NMR spectrum, δ, ppm: 1.23 t (3H),
4.14–4.23 m (2H), 5.09 s (1H), 7.27–7.70 m (4H).
Found, %: C 60.04; H 4.68. C16H15FO4S. Calculated,
%: C 59.62; H 4.69.
Ethyl 1-naphthyl(phenylsulfonyl)acetate
PhSO2CH(CO2Et)C10H7-1 was obtained from 104 mg
of 1-bromonaphthalene and 148 mg of ethyl phenyl-
sulfonylacetate. Yield 110 mg, yellowish oily sub-
stance. 13C NMR spectrum, δ, ppm: 13.8, 62.5, 69.15,
122.36, 123.7, 124.83, 125.85, 127.0, 128.38, 128.47,
128.57, 128.89, 129.85, 130.31, 131.74, 133.65,
133.98, 136.39, 165.14. Found, %: C 68.02; H 5.24.
C17H18O5S. Calculated, %: C 67.78; H 5.12.
Ethyl phenylsulfonyl(4-trifluoromethylphenyl)-
acetate PhSO2CH(CO2Et)C6H4CF3-4 was obtained
from 112 mg of 4-bromobenzotrifluoride and 148 mg
of ethyl phenylsulfonylacetate. Yield 154 mg, colorless
crystals, mp 94–95°C (from hexane). IR spectrum, ν,
cm–1: 1151, 1330 (SO2); 1726, 1737 (CO2). 13C NMR
spectrum, δC, ppm: 13.8, 62.8, 74.7, 123.7 q, 125.4,
128.8, 129.8, 130.8, 131.7, 131.7 q, 134.5, 136.3,
164.2. Mass spectrum, m/z: 372 (M+), 353, 326, 303,
231, 203, 186, 175, 159, 141. Found, %: C 55.04;
H 4.18. C17H15F3O4S. Calculated, %: C 54.84; H 4.03.
Ethyl 4-methoxyphenyl(phenylsulfonyl)acetate
PhSO2CH(CO2Et)C6H4OMe-4. Colorless crystals,
mp 75–77°C. IR spectrum, ν, cm–1: 1149, 1322 (SO2);
1
1739 (CO2). H NMR spectrum, δ, ppm: 1.23 t (3H),
3.80 s (3H), 4.12–4.27 m (2H), 5.04 s (1H), 6.82 d
(2H), 7.27 d (2H), 7.44 t (2H), 7.59–7.64 m (3H).
Found, %: C 60.84; H 5.31. C17H18O5S. Calculated, %:
C 61.06; H 5.43.
Ethyl 4-methylphenyl(phenylsulfonyl)acetate
PhSO2CH(CO2Et)C6H4CH3-4 was obtained from
86 mg of 4-bromotoluene and 148 mg of ethyl
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

MITIN et al.
810
(1H), 7.05–7.1 m (2H), 7.20–7.29 m (2H), 7.487 t
(4H), 7.650 t (2H), 7.785 d (4H). Found, %: C 58.28;
H 3.68. C19H15FO4S2. Calculated, %: C 58.45; H 3.87.
Ethyl phenylsulfonyl(trans-2-phenylvinyl)acetate
PhSO2CH(CO2Et)CH=CHPh-trans was obtained
from 91 mg of trans-β-bromostyrene and 148 mg of
ethyl phenylsulfonylacetate. Yield 70 mg, colorless
oily substance. 1H NMR spectrum, δ, ppm: 1.25 t (3H),
4.22 q (2H), 4.68 d (1H, J = 9.5 Hz), 6.15 d.d (1H, J1 =
9.5, J2 = 16 Hz), 6.58 d (1H, J = 16 Hz), 7.28–7.34 m
(5H), 7.53 t (2H), 7.67 t (1H), 7.86 d (2H). 13C NMR
spectrum, δC, ppm: 13.9, 62.5, 74.6, 115.8, 126.9,
128.6, 128.8, 128.9, 129.7, 134.2, 135.3, 136.9, 139.5,
164.7. Found, %: C 65.79; H 5.51. C18H18O4S. Calcu-
lated, %: C 65.43; H 5.49.
3-Thienylbis(pheny lsulf onyl)methane
3-C4H3SCH(SO2Ph)2 was obtained from 88 mg of
3-bromofluorobenzene and 175 mg of bis(phenyl-
sulfonyl)methane. Yield 158 mg, colorless crystals,
1
mp 185–186°C. H NMR spectrum, δ, ppm: 5.606 s
(1H), 7.00 d (1H), 7.22 d (1H), 7.315 s (1H), 7.47 t
(4H), 7.63 t (2H), 7.77 d (4H). Found, %: C 54.27;
H 3.91. C17H14O4S3. Calculated, %: C 53.95; H 3.73.
2 -Pyri dyl bis( phe nyls ulf onyl)met ha ne
2-PyCH(SO2Ph)2 was obtained from 79 mg of
3-bromopyridine and 175 mg of bis(phenylsulfonyl)-
methane. Yield 168 mg, colorless crystals, mp 202–
Ethyl phenylsulfonyl(3-pyridyl)acetate
PhSO2CH(CO2Et)Py-3 was obtained from 79 mg of
3-bromopyridine and 148 mg of ethyl phenylsul-
fonylacetate. Yield 78 mg, colorless oily substance.
1H NMR spectrum, δ, ppm: 1.23 t (3H), 4.15–4.28 m
(2H), 5.122 s (1H), 7.30 t (1H), 7.49 t (2H), 7.63–
7.69 m (3H), 7.97 t (1H), 8.415 s (1H), 8.62 d (1H).
Found, %: C 59.34; H 5.01. C15H15NO4S. Calculated,
%: C 59.00; H 4.95.
1
203°C. H NMR spectrum, δ, ppm: 5.455 s (1H),
7.78 d (4H), 7.50 t (4H), 7.66 t (2H), 8.20 br (1H),
8.61 d (1H). Found, %: C 58.03; H 4.06; N 3.99.
C21H15F3O3S2. Calculated, %: C 57.89; H 4.05; N 3.75.
1-Naphthylbis(phenylsulfonyl)methane
1-C10H7CH(SO2Ph)2 was obtained from 104 mg of
1-bromonaphthalene and 175 mg of bis(phenyl-
sulfonyl)methane. Yield 163 mg, colorless crystals,
Phenylsulfonyl(4-trifluoromethylphenyl)nitro-
methane PhSO2CH(NO2)C6H4CF3-4 was obtained
from 112 mg of 4-brombenzotrifluoride and 130 mg of
ethyl phenylsulfonylacetate. Yield 123 mg, colorless
1
mp 171–172°C (from MeOH). H NMR spectrum, δ,
1
ppm: 6.462 s (1H), 7.33–7.87 m (6H), 7.43 t (2H),
7.50 t (3H), 7.75 d (4H), 7.86 d (1H), 8.05 d (1H).
Found, %: C 65.62; H 4.36. C23H18O4S2. Calculated,
%: C 65.38; H 4.29.
crystals, mp 110–112°C. H NMR spectrum, δ, ppm:
6.545 s (1H), 7.567 t (2H), 7.654 d (2H), 7.68 d (2H),
7.73–7.78 m (3H). Found, %: C 55.98; H 3.91.
C13H11NO4S. Calculated, %: C 56.31; H 4.00.
3-Quinolylbis(phenylsulfonyl)methane
3-C9H6NCH(SO2Ph)2 was obtained from 105 mg of
3-bromoquinoline and 175 mg of bis(phenylsulfonyl)-
methane. Yield 161 mg, colorless crystals, mp 228–
1-Phenyl-2-phenylsulfonyl-2-(4-trifluoromethyl-
phenyl)ethanone PhSO2CH(COPh)C6H4CF3-4 was
obtained from 112 mg of 4-bromobenzotrifluoride and
170 mg of phenylsulfonylacetophenone. Yield 61 mg,
colorless crystals, mp 142.5–143.5°C. IR spectrum, ν,
1
229°C. H NMR spectrum, δ, ppm: 5.655 s (1H),
1
cm–1: 1159, 1324 (SO2); 1672 m (C=O). H NMR
7.477 t (4H), 7.60–7.68 m (3H), 7.77–7.86 m (6H).
Found, %: C 62.57; H 4.22; N 3.08. C22H17NO4S2.
Calculated, %: C 62.39; H 4.05; N 3.31.
spectrum, δ, ppm: 6.208 s (1H), 7.41–7.48 m (4H),
7.51–7.59 m (5H), 7.62–7.67 m (3H), 7.88 d (2H).
Found, %: C 62.52; H 3.75. C21H15F3O3S. Calculated,
%: C 62.37; H 3.73.
Methylsulfonyl(phenylsulfonyl)(4-trifluoro-
methylphenyl)methane 4-CF3C6H4CH(SO2Ph)-
SO2Me was obtained from 112 mg of 4-bromobenzo-
trifluoride and 175 mg of methylsulfonyl(phenyl-
sulfonyl)methane. Yield 155 mg, colorless crystals,
4-Trifluoromethylphenylbis(phenylsulfonyl)-
methane 4-CF3C6H4CH(SO2Ph)2 was obtained from
112 mg of 4-bromobenzotrifluoride and 175 mg of bis-
(phenylsulfonyl)methane. Yield 187 mg, colorless
crystals, mp 210–211°C. Found, %: C 54.81; H 3.51.
C20H15F3O4S2. Calculated, %: C 54.54; H 3.43.
1
mp 195–196°C. H NMR spectrum, δ, ppm: 3.443 s
(3H), 5.376 s (1H), 7.44–7.51 m (4H), 7.59 d (2H),
7.62–7.70 m (3H). Found, %: C 47.81; H 3.58.
C15H13F3O4S2. Calculated, %: C 47.61; H 3.46.
3-Fluorophenylbis(phenylsulfonyl)methane
3-FC6H4CH(SO2Ph)2 was obtained from 88 mg of
3-bromofluorobenzene and 175 mg of bis(phenyl-
sulfonyl)methane. Yield 158 mg, colorless crystals,
Ethyl (4-trifluoromethylphenyl)(2-phenylethyl-
sulfonyl)acetate 4-CF3C6H4CH(COOEt)SO2CH2-
CH2Ph was obtained from 112 mg of 4-bromoben-
zotrifluoride and 166 mg of ethyl (2-phenylethyl-
1
mp 207.5–209°C. H NMR spectrum, δ, ppm: 5.395 s
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

PALLADIUM-CATALYZED ARYLATION OF SULFONES
811
sulfonyl)acetate. Yield 150 mg, colorless crystals,
mp 133–134°C (iz EtOH). 1H NMR spectrum, δ, ppm:
1.321 t (3H), 3.252 m (2H), 3.548–3.645 m (2H),
4.272–4.369 m (2H), 4.956 s (1H), 7.183 d (2H),
7.230–7.343 m (3H), 7.682 s (4H). Found, %: C 57.11;
H 4.89. C19H19F3O4S. Calculated, %: C 56.99; H 4.78.
6.66 s (1H). Found, %: C 40.46; H 2.32; S 6.92.
C15H5F11O2S. Calculated, %: C 40.29; H 2.03; S 7.16.
Reaction of sulfones with aryl halides, followed
by treatment with electrophile. A reactor was
charged in a stream of argon with 0.5 mmol of the
corresponding sulfone, 15.8 mg (12 mol %) of tri-
phenylphosphine, 10.4 mg (2 mol %) of Pd2dba3·
CHCl3, 10–20 mg (1.5 mmol) of naphthalene (internal
standard), 60 mg of sodium hydride (a 60% suspension
in oil), and 0.5 mmol of aryl halide. The reactor was
cooled with liquid nitrogen and evacuated, and 4 ml of
1,4-dioxane was recondensed thereto. The mixture was
degassed by triple freeze–thaw procedure, and the
reactor was filled with argon. The mixture was then
stirred at 70°C, the progress of the reaction being
monitored by GLC and TLC (Silufol UV-254). When
the reaction was complete, the mixture was cooled
with ice water, 1 mmol of electrophilic reagent
(N-chlorosuccinimide or allyl acetate) was added, and
the mixture was stirred at 30°C (TLC, Silufol UV-
254). The mixture was diluted with water and treated
with diethyl ether (3×10 ml). The extract was filtered
and evaporated, and the residue was subjected to
chromatography on silica gel (40–100 µm) using ethyl
acetate–petroleum ether (bp 65–68°C) as eluent.
Ethyl cyclohexylsulfonyl(4-trifluoromethyl-
phenyl)acetate 4-CF3C6H4CH(COOEt)SO2C6H13-
cyclo was obtained from 112 mg of 4-bromobenzo-
trifluoride and 152 mg of ethyl cyclohexylsulfonyl-
acetate. Yield 125 mg, colorless oily substance.
1H NMR spectrum, δ, ppm: 1.20–1.70 m (9H), 1.90–
2.00 m (2H), 2.20–2.35 m (2H), 3.50–3.65 t.d (1H),
4.37–4.47 m (2H), 5.71 s (1H), 7.70 d (2H), 7.90 d
(2H). Found, %: C 54.09; H 5.74. C17H21F3O4S.
Calculated, %: C 53.96; H 5.59.
Phenyl(4-trifluoromethylphenyl)(trifluoro-
methylsulfonyl)methane 4-CF3C6H4CH(Ph)SO2CF3
was obtained from 112 mg of p-bromobenzotrifluoride
and 112 mg of benzyl trifluoromethyl sulfone. Yield
1
123 mg, colorless oily substance. H NMR spectrum,
δ, ppm: 7.10–7.19 m (3H), 6.985 d (2H), 5.673 s (1H).
Found, %: C 48.71; H 2.98; S 8.93. C15H10F6O2S.
Calculated, %: C 48.92; H 2.74; S 8.71.
Pentafluorophenyl(4-trifluoromethylphenyl)-
(trifluoromethylsulfonyl)methane 4-CF3C6H4CH-
(C6F5)SO2CF3 was obtained from 112 mg of p-bromo-
benzotrifluoride and 112 mg of pentafluorobenzyl tri-
fluoromethyl sulfone. Yield 184 mg, colorless oily
Chloro(methylsulfonyl)(phenylsulfonyl)(4-tri-
fluoromethylphenyl)methane 4-CF3C6H4CCl-
(SO2Ph)(SO2Me) was obtained from 112 mg of
4-brombenzotrifluoride, 118 mg of methylsulfonyl-
(phenylsulfonyl)methane, and 133 mg of NCS. Yield
168 mg, colorless crystals, mp 135–136°C (from
1
substance. H NMR spectrum, δ, ppm: 7.785 d (2H),
7.730 d (2H), 6.055 s (1H). Found, %: C 48.71;
H 1.33; S 6.79. C15H5F11O2S. Calculated, %: C 39.32;
H 1.10; S 7.00.
1
EtOH). H NMR spectrum, δ, ppm: 3.582 s (3H),
7.412 t (2H), 7.512 d (2H), 7.63–7.68 m (3H), 8.08 d
(2H). Found, %: C 43.81; H 3.10. C15H12ClF3O4S2.
Calculated, %: C 43.64; H 2.91.
(3-Bromophenyl)(4-trifluoromethylphenyl)(tri-
fluoromethylsulfonyl)methane 4-CF3C6H4CH-
(SO2CF3)C6H4Br-3 was obtained from 112 mg of
p-bromobenzotrifluoride and 190 mg of 3-bromoben-
zyl trifluoromethyl sulfone. Yield 66 mg, colorless oily
Ethyl chloro(2-phenylethylsulfonyl)(4-trifluoro-
methylphenyl)acetate 4-CF3C6H4CCl(COOEt)SO2-
CH2CH2Ph was obtained from 112 mg of 4-bromo-
benzotrifluoride and 128 mg of ethyl (2-phenylethyl-
sulfonyl)acetate. Yield 156 mg, colorless oily sub-
1
substance. H NMR spectrum [(CD3)2CO], δ, ppm:
8.107 d (2H), 8.041 s (1H), 7.914 m (3H), 7.530 t
(1H), 7.723 d (1H), 6.66 s (1H). Found, %: C 40.20;
H 2.21; S 6.99. C15H5F11O2S. Calculated, %: C 40.29;
H 2.03; S 7.16.
1
stance. H NMR spectrum, δ, ppm: 1.344 t (3H),
3.197 t (2H), 3.68–3.88 m (2H), 4.414 q (2H), 7.21–
7.29 m (5H), 7.334 t (2H), 7.725 d (2H), 7.864 d (2H).
Found, %: C 52.56; H 4.19. C19H18ClF3O4S. Calcu-
lated, %: C 52.48; H 4.17.
(4-Bromophenyl)(4-trifluoromethylphenyl)(tri-
fluoromethylsulfonyl)methane 4-CF3C6H4CH-
(SO2CF3)C6H4Br-3 was obtained from 112 mg of
p-bromobenzotrifluoride and 190 mg of 4-bromoben-
zyl trifluoromethyl sulfone. Yield 79 mg, colorless oily
Ethyl chloro(cyclohexylsulfonyl)(4-trifluoro-
methylphenyl)acetate [4-CF3C6H4CCl(COOEt)SO2-
C6H13-cyclo was obtained from 112 mg of 4-bromo-
benzotrifluoride, 118 mg of ethyl cyclohexylsulfonyl-
acetate, and 133 mg of NCS. Yield 128 mg, colorless
1
substance. H NMR spectrum [(CD3)2CO], δ, ppm:
8.107 d (2H), 8.041 s (1H), 7.90 d (2H), 7.50 d (2H),
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004

MITIN et al.
812
1
oily substance. H NMR spectrum, δ, ppm: 1.354 t
(3H), 1.17–2.35 m (10H), 3.80–3.92 t.d (1H), 4.37–
4.47 m (2H), 7.695 d (2H), 7.905 d (2H). Found, %:
C 49.56; H 4.99. C17H20ClF3O4S. Calculated, %:
C 49.46; H 4.88.
12 h at 70°C (oil bath) under argon. According to the
1
GLC, TLC, and H and 19F NMR data, no reaction
occurred. An additional amount of sodium hydride
(preliminarily washed with hexane and dried, 11 mg of
a 60% suspension in oil) was added, ad the mixture
was stirred for 3 h at 70°C under argon. According to
the GLC, TLC, and 1H and 19F NMR data, the reaction
was complete.
4,4-Bis(phenylsulfonyl)-4-(3-pyridyl)-1-butene
CH2=CHCH2C(Py-3)(SO2Ph)2 was obtained from
79 mg of 3-bromopyridine, 148 mg of bis(phenyl-
sulfonyl)methane, and 100 mg of allyl acetate. Yield
1
REFERENCES
140 mg, colorless oily substance. H NMR spectrum,
δ, ppm: 8.19–8.21 m (1H), 8.61 d (1H), 7.78 d (4H),
7.66 t (2H), 7.50 t (4H), 5.0–5.6 m (3H), 2.35–2.62 m
(2H). Found, %: C 61.23; H 4.84; N 3.50.
C21H19NO4S2. Calculated, %: C 61.00; H 4.63; N 3.39.
1. Prilezhaeva, E.N., Poluchenie i svoistva organicheskikh
soedinenii sery (Synthesis and Properties of Organic
Sulfur Compounds), Belen’kii, L.I., Ed., Moscow:
Khimiya, 1998, p. 115.
Ethyl 1-phenylsulfonyl-1-(4-trifluoromethyl-
phenyl)-3-pentenoate CH2=CHCH2C(SO2Ph)-
(CO2Et)C6H4CF3-4 was obtained from 112 mg of
4-bromobenzotrifluoride, 114 mg of ethyl phenylsul-
fonylacetate, and 100 mg of allyl acetate. Yield
2. Najera, C. and Yus, M., Tetrahedron, 1999, vol. 55,
p. 10546.
3. Houben–Weyl. Methoden der organische Chemie,
Stuttgart: Georg Thieme, 1985, E11.
4. Kashin, A.N., Mitin, A.V., Beletskaya, I.P., and Wife, R.,
1
Tetrahedron Lett., 2002, vol. 43, p. 2539.
165 mg, colorless oily substance. H NMR spectrum,
δ, ppm: 7.6–7.9 m (8H), 7.43 t (1H), 5.0–5.6 m (3H),
4.41–4.43 m (2H), 2.35–2.62 m (2H), 1.23 t (3H).
Found, %: C 58.26; H 4.68. C20H19F3O4S. Calculated,
%: C 58.24; H 4.64.
5. Culkin, D.A. and Hartwig, J.F., Acc. Chem. Res., 2003,
vol. 36, p. 234.
6. Prim, D., Campagne, J.-M., Joseph, D., and Andriolet-
ti, B., Tetrahedron, 2002, vol. 58, p. 2041.
7. Sakamoto, T., Katoh, E., Kondo, Y., and Yamanaka, H.,
Ethyl 4,9-dimethyl-1-phenylsulfonyl-1-(4-tri-
fluoromethylphenyl)-3,7-decadienoate was obtained
from 112 mg of 4-bromobenzotrifluoride, 114 mg of
ethyl phenylsulfonylacetate, and 196 mg of geranyl
acetate. Yield 185 mg, colorless oily substance.
1H NMR spectrum, δ, ppm: 7.6–7.9 m (8H), 7.44 t
(1H), 5.0–5.1 m (2H), 4.41–4.43 m (2H), 1.5–2.6 m
(18H). Found, %: C 63.49; H 6.38. C27H31F3O4S.
Calculated, %: C 63.76; H 6.14.
Chem. Pharm. Bull., 1990, vol. 38, p. 1513.
8. Uno, M., Seto, K., and Takahashi, S., J. Chem. Soc.,
Chem. Commun., 1984, p. 932.
9. Bordwell, F.G. and Hughes, D.L., J. Org. Chem., 1980,
vol. 45, p. 3314; Bordwell, F.G. and Hughes, D.L.,
J. Org. Chem., 1980, vol. 45, p. 3320.
10. Bordwell, F.G., Vanier, W.S., Matthews, W.S., Hendrick-
son, J.B., and Skipper, P.L., J. Am. Chem. Soc., 1975,
vol. 97, p. 7160.
Study of the reaction of ArPdL2CH complexes
with carbanions. Preliminarily washed with hexane
and dried sodium hydride, 11 mg (a 60% suspension in
oil), was added with stirring under argon to a solution
of 57 mg (0.25 mmol) of ethyl phenylsulfonylacetate
and 10 mg of durene (internal standard) in 10 ml of
dioxane or THF-d8. The mixture was stirred until
hydrogen no longer evolved, filtered under argon, and
transferred into a reactor; a sample of the mixture was
11. Nelson, R.B. and Gribble, G.W., J. Org. Chem., 1974,
vol. 39, p. 1425.
12. Ishii, Y., Ann. N.Y. Acad. Sci., 1972, vol. 239, p. 114;
Ukai, T., Kawazura, H., and Ishii, Y., J. Organomet.
Chem., 1974, vol. 65, p. 253.
13. Kohler, E.P. and Tishler, M., J. Am. Chem. Soc., 1935,
vol. 57, p. 217.
14. Ashley, W.C. and Shriner, R.L., J. Am. Chem. Soc.,
1932, vol. 54, p. 4410.
1
analyzed by H and 19F NMR spectroscopy. To the
15. Hendrickson, J.B., Giga, A., and Wareing, J., J. Am.
Chem. Soc., 1974, vol. 96, p. 2275.
resulting carbanion solution we added with stirring
under argon 214 mg (0.25 mmol) of the complex
4-CF3C6H4Pd(PPh3)2Br. The solution was stirred for
16. Fitton, P. and Rick, E.A., J. Organomet. Chem., 1971,
vol. 28, p. 279.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 40 No. 6 2004