Palladium-catalyzed alkenyl C-H bond sulfonylation reaction using organosulfonyl chlorides

Article abstract of DOI:10.1016/j.tet.2013.01.071

A Pd-catalyzed alkenyl C-H bond direct sulfonylation of vinyl pyridine and enamides was developed. Various arylsulfonyl chlorides were tested in this reaction and the desired products were obtained in good yields. Moreover, the alkyl sulfonyl chloride could also be used though the yield was lower. A possible Pd(II)/Pd(IV) catalytic pathway involved in this coupling reaction was proposed.

Full text of DOI:10.1016/j.tet.2013.01.071

Tetrahedron 69 (2013) 4403e4407
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Palladium-catalyzed alkenyl CeH bond sulfonylation reaction using
organosulfonyl chlorides
,b,
Yun-He Xu a, Min Wang a, Ping Lu a, Teck-Peng Loh a
*
a Department of Chemistry, University of Science and Technology of China, Hefei 230026, China
b Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371,
Singapore
a r t i c l e i n f o
a b s t r a c t
Article history:
A Pd-catalyzed alkenyl CeH bond direct sulfonylation of vinyl pyridine and enamides was developed.
Various arylsulfonyl chlorides were tested in this reaction and the desired products were obtained in
good yields. Moreover, the alkyl sulfonyl chloride could also be used though the yield was lower. A
possible Pd(II)/Pd(IV) catalytic pathway involved in this coupling reaction was proposed.
Ó 2013 Elsevier Ltd. All rights reserved.
Received 19 November 2012
Received in revised form 15 January 2013
Accepted 23 January 2013
Available online 18 February 2013
Keywords:
Palladium
Coupling
Vinyl pyridine
Enamide
Sulfonylation
1. Introduction
palladium catalysts in dioxane with 0.5 equiv of K2CO3. The best
result (product in 71% yield) was obtained with 10 mol %
Organosulfones are important synthetic intermediate in organic
chemistry.1 Therefore, the preparation of organosulfur has gained
much attention.2 Among the methods developed, the addition of
sulfonyl radicals generated from the sulfonyl halides to olefins is
one of the most common methods.3 Kharasch reported the first
example of addition of sulfuryl chloride induced by peroxide into
the olefinic double bond.4 Since then a number of arenesulphonyl
halides and alkaneesulphonyl chlorides were added to olefins by
the reduction with metallic reagents at high temperature,5 or ex-
posure to uv light.6 In 2004, palladium-catalyzed coupling reaction
of aryl boronic acids with arylsulfonyl chloride was developed by
professor Bandgar.7 Recently, palladium-mediated CeH activation/
cross-coupling of 2-phenyl pyridine and derivatives with arylsul-
fonyl chlorides was elegantly disclosed by Dong.8 Due to our recent
interest in the development of palladium-catalyzed alkenyl CeH
bond functionalization reaction,9 herein, we report a sulfonylation
reaction of olefins generated by coupling with organosulfonyl
chloride and catalyzed by palladium.
Pd(PhCN)2Cl2; both Pd(CH3CN)2Cl2 and Pd(OAc)2 also could af-
ford the desired product in moderate yields, but only low yield
was obtained when the Pd(TFA)2 (Table 1, entry 3) or Pd(acac)2
(Table 1, entry 4) was used as catalyst. It was noted that im-
proving the amount or decreasing the use of K2CO3 would lower
the product’s yield (Table 1, entry 8). Other bases such as Na2CO3
(Table 1, entry 9) or K3PO4 (Table 1, entry 10) applied in this
reaction could also provide the product in moderate yield also,
while low yields were obtained when organic bases like trie-
thylamine (Table 1, entry 11) or pyridine (Table 1, entry 12) was
used. It was further found that the choice of solvent was crucial
important for this reaction, no any desired product was formed
when the reaction was carried in DMF or THF (Table 1, entry 15,
16, respectively). Only recovery of the starting materials was
found in the control experiment in the absence of palladium
catalyst (Table 1, entry 13).
Next, in the presence of 10 mol % Pd(PhCN)2Cl2 and 0.5 equiv of
ꢀ
ꢀ
K2CO3 in dioxane with 4 A m s and heating under 120 C, the scope
of the sulfonyl chloride was examined. The results are shown as in
Table 2. We found that not only the arylsulfonyl chloride with
electron-donating groups but also the substrates containing even
strong electron-withdrawing groups all could afford the corre-
sponding products in reasonable yields. Notably, 25% yield of
product could be obtained when 1-butanesulfonyl chloride was
used to react with 2-(prop-1-en-2-yl)pyridine (Table 2, 3g). The
2. Results and discussion
Initially, 2-(prop-1-en-2-yl)pyridine as substrate was chosen
to investigate the conditions. We first examined different
* Corresponding author. E-mail address: teckpeng@ntu.edu.sg (T.-P. Loh).
0040-4020/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2013.01.071

4404
Y.-H. Xu et al. / Tetrahedron 69 (2013) 4403e4407
Table 1
Table 3
Optimization of the coupling reaction condition of
a
-methyl vinyl pyridine with p-
Palladium-catalyzed sulfonylation of vinyl pyridine derivatives and enamides
toluene sulfonyl chloridea
Entry
Cat/mol %
Base/equiv
Solvent
Time/h
Yield (%)
1
2
3
4
5
6
7
8
Pd(CH3CN)2Cl2/10
Pd(OAc)2/10
Pd(TFA)2/10
Pd(acac)2/10
PdCl2/10
Pd(PhCN)2Cl2/10
Pd(PhCN)2Cl2/10
Pd(PhCN)2Cl2/10
Pd(PhCN)2Cl2/10
Pd(PhCN)2Cl2/10
Pd(PhCN)2Cl2/10
Pd(PhCN)2Cl2/10
d
K2CO3/0.5
K2CO3/0.5
K2CO3/0.5
K2CO3/0.5
K2CO3/0.5
K2CO3/0.5
K2CO3/0.2
K2CO3/2
Na2CO3/0.5
K3PO4/0.5
Et3N/0.5
Pyridine/0.5
K2CO3/0.5
K2CO3/0.5
K2CO3/0.5
K2CO3/0.5
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
Dioxane
DMF
24
24
24
24
24
24
24
24
24
24
24
24
24
48
24
24
59
65
26
13
60
71
51
40
61
52
34
25
d
9
10
11
12
13
14
15
16
Conditions for vinylpyridine derivatives: 1 (0.2 mmol) and 2
(0.3 mmol), Pd(PhCN)2Cl2 (10 mol%), K2CO3 (0.1 mmol) and 50
mg 4Å molecular sieves in dioxane (1 ml) were heated for 24 h at
120 ° . Conditons for enamides: 1 (0.2 mmol) and 2 (0.3 mmol),
Pd(CH3CN)2Cl2 (10 mol%), K2CO3 (0.1 mmol) and 50 mg 4Å
molecular sieves in dioxane (1 ml) were heated for 24 h at 120
°
Pd(PhCN)2Cl2//10
Pd(PhCN)2Cl2/10
Pd(PhCN)2Cl2/10
32
d
THF
d
a
Conditions:
a-methyl vinyl pyridine (0.2 mmol) and sulfonyl chloride
ꢀ
(0.3 mmol), Pd(II) (10 mol %), base and 50 mg 4 A molecular sieves in corresponding
solvent (1 ml) were heated at 120 ꢀC.
Table 2
comparable low yields were obtained for the substrates with halide
substituent. It was also found that chromenone-derivatived
enamide could afford the desired product in 33% yield (Table 3, 4i).
A possible mechanism for the olefinic CeH bond sulfonylation
reaction is proposed as shown in Scheme 1. Firstly the olefin
reacted with Pd(II) under the basic condition to give a cyclic
vinylpalladium species A or B, then the five-, or six-membered
palladacyclic intermediate reacted with the sulfonyl chloride and
a new Pd(IV) complex C was generated via an oxidation.10 After
a reductive elimination, the Pd(II) catalyst was involved again into
the next catalytic cycle (Scheme 1).
Sulfonylation of a-methyl vinyl pyridine with various sulfonyl chlorides
Conditions: α-methyl vinylpyridine (0.2 mmol) and sulfonyl
chloride (0.3 mmol), Pd(PhCN)2Cl2 (10 mol%), K2CO3 (0.1
mmol) and 50 mg 4Å molecular sieves in dioxane (1 ml) were
heated for 24 h at 120 ° .
tolerance of halides substituents on the phenyl ring permits pos-
sible further transformation of the product.
Scheme 1. Proposed mechanism for the sulfonylation of olefins.
Other functionalized olefins were found to be compatible with
this protocol (Table 3). The substituent on the pyridine ring affects
the yield dramatically. The electron-donating group such as methyl
group slightly decreased the yield. On the basis of this result, we
tested the enamide scope for this reaction under slightly modified
conditions. It was found some differences happened comparing
with the previous results, only the arylsulfonyl chloride with
electron-donating groups could afforded the products in high
yields. The indanone-derivatived enamides with electro-donating
groups easily gave the products in good yields, while only
3. Conclusion
In conclusion, we have developed a Pd-catalyzed alkenyl CeH
bond direct sulfonylation of vinyl pyridine and enamides. Various
arylsulfonyl chlorides were tested in this reaction and the desired
products were obtained in good yields. A possible Pd(II)/Pd(IV)
catalytic pathway involved in this coupling reaction was proposed.
Further study focused on extending the scope and establishing the
exact mechanism are currently underway in this laboratory.

Y.-H. Xu et al. / Tetrahedron 69 (2013) 4403e4407
4405
4. Experimental section
4.1. General
J¼7.84 Hz, 1H), 7.48 (d, J¼7.84 Hz, 1H), 7.23e7.26 (m, 2H), 6.98 (d,
J¼9.00 Hz, 2H), 3.85 (s, 3H), 2.57 (s, 3H); 13C NMR (100 MHz, CDCl3)
d
163.5, 155.8, 149.3, 149.1, 136.9, 133.5, 130.2, 129.6, 124.2, 121.1,
55.7, 14.9; IR (film, cmꢁ1): 3020, 1595, 1579, 1568, 1496, 1431, 1315,
1296, 1261, 1141, 1026; HRMS m/z calculated for C15H16NO3S
[MþH]þ: 290.0851; found 290.0849.
All commercially obtained reagents for the cross-coupling re-
action were used as received: anhydrous dioxane was obtained
from SigmaeAldrich and used as received. The enamides and vinyl
pyridines were prepared according to the reported references.11 All
cross-coupling reactions were run under 1 atm O2 and no pre-
cautions taken to exclude moisture. Thin-layer chromatography
(TLC) was conduced with Merck 60 F254 precoated silicon gel plate
(0.2 mm thickness) and visualized with UV and potassium per-
manganate staining, followed by heating on the hot plate. Flash
chromatography was performed using Merck silica gel 60 with
distill solvents. 1H NMR spectra were performed on a Brucker Ad-
vance 300, 400 NMR spectrometer and are reported in parts per
4.2.4. Compound 3d. This compound was prepared by the general
procedure and was obtained as
a
white solid. Yield¼64%.
Mp¼102e104 ꢀC; Rf¼0.33 (EA/Hexane¼3:7). 1H NMR (400 MHz,
CDCl3)
d
8.69 (d, J¼8.60 Hz, 1H), 8.53 (d, J¼4.60 Hz, 1H), 8.43 (d,
J¼7.36 Hz, 1H), 8.09 (d, J¼8.24 Hz, 1H), 7.93 (d, J¼8.12 Hz, 1H),
7.55e7.69 (m, 4H), 7.45e7.47 (m, 2H), 7.21e7.26 (m, 1H), 2.60 (s,
3H); 13C NMR (100 MHz, CDCl3)
d 155.5, 150.2, 149.4, 136.9, 136.8,
134.9, 134.2, 130.2, 129.2, 129.1, 128.7, 128.4, 126.9, 124.5, 124.3,
124.2, 121.0, 15.2; IR (film, cmꢁ1): 3018,1618, 1581, 1564, 1508, 1465,
1431, 1305, 1215, 1155, 1124; HRMS m/z calculated for C18H16NO2S
[MþH]þ: 310.0902; found 310.0900.
million downfield from SiMe4 (d 0.0) and relative to the signal of
chloroform-d (J¼7.26, singlet). Data reported as: s¼singlet,
d¼doublet, t¼triplet, q¼quartet, m¼multiplet, coupling con-
stant(s) in Hertz; integration. Proton-decoupled 13C NMR spectra
were recorded on a Bruker Advance 300 (75 MHz), Bruker Advance
400 (100 MHz) spectrometer and are reported in ppm using solvent
as an internal standard (CDCl3 at 77.23 ppm). IR spectra were
recorded as thin films on NaCl plates on a Bio-Rad FTS 165 FTIR
spectrometer and are reported in frequency of absorption (cmꢁ1).
High resolution mass spectral analysis (HRMS) was performed on
Waters Q-Tof Premier Mass Spectrometer.
4.2.5. Compound 3e. This compound was prepared by the general
procedure and was obtained as
a
white solid. Yield¼60%.
Mp¼63e65 ꢀC; Rf¼0.37 (EA/Hexane¼3:7). 1H NMR (400 MHz,
CDCl3)
d
8.57 (d, J¼4.16 Hz, 1H), 8.12 (d, J¼7.84 Hz, 1H), 7.71 (t,
J¼7.74 Hz, 2H), 7.45e7.51 (dd, J¼8.00, 7.44 Hz, 2H), 7.36 (t,
J¼7.60 Hz,1H), 7.25e7.31 (m, 3H), 2.65 (s, 3H), 2.50 (s, 3H); 13C NMR
(100 MHz, CDCl3)
d 155.6, 150.2, 149.4, 139.8, 137.9, 137.0, 133.3,
132.5, 129.5, 128.7, 126.3, 124.3, 121.0, 20.4, 15.1; IR (film, cmꢁ1):
3020, 1639, 1465, 1431, 1305, 1215, 1149, 1058; HRMS m/z calculated
for C15H16NO2S [MþH]þ: 274.0902; found 274.0901.
4.2. General procedures for direct cross-coupling reaction of
a
-methyl vinyl pyridines with p-toluene sulfonyl chloride
4.2.6. Compound 3f. This compound was prepared by the general
4.2.1. Compound 3a. A 10 ml dried round bottom flask was charged
sequentially with stirring bar, Pd(PhCN)2Cl2 (0.02 mmol,
10 mol %), K2CO3 (05 equiv), p-toluene sulfonyl chloride (1.5 equiv)
procedure and was obtained as
a
white solid. Yield¼56%.
a
Mp¼65e67 ꢀC; Rf¼0.30 (EA/Hexane¼3:7).1H NMR (400 MHz, CDCl3)
d
8.58 (d, J¼4.48 Hz, 1H), 7.91 (d, J¼8.52 Hz, 2H), 7.71 (td, J¼7.76,
1.40 Hz,1H), 7.51 (d, J¼8.4 Hz, 3H), 7.26e7.29 (m, 2H), 2.59 (s, 3H); 13C
ꢀ
and 4 A molecular sieve (50 mg). Dry dioxane (1 ml) and a-methyl
vinyl pyridine (0.2 mmol, 1 equiv) were added into the mixture in
sequence, and the resultant mixture was stirred at 120 ꢀC under
1 atm of oxygen (balloon pressure) for 24 h. After cooling down, the
mixture was diluted with ethyl acetate and filtered via Celite. After
removing the organic solvent under reduced pressure, the crude
product was purified by silica gel flash column chromatography
(EtOAc/hexane mixtures). And 3a was obtained in 71% yield as
a white solid. Mp¼98e99 ꢀC; Rf¼0.35 (EA/Hexane¼3:7). 1H NMR
NMR (100 MHz, CDCl3) d 155.4,150.6,149.4,140.4,140.0,137.0,129.5,
129.2,128.9,124.5,121.1,15.1; IR (film, cmꢁ1): 3020,1612,1581,1568,
1465, 1431, 1394, 1315, 1215, 1147, 1085, 1014; HRMS m/z calculated
for C14H13NO2SCl [MþH]þ: 294.0356; found 294.0350.
4.2.7. Compound 3g. This compound was prepared by the general
procedure and was obtained as a yellow oil. Yield¼25%. Rf¼0.4 (EA/
Hexane¼3:7). 1H NMR (300 MHz, CDCl3)
d 8.63e8.65 (m, 1H), 7.76
(300 MHz, CDCl3)
d
8.58 (d, J¼4.23 Hz, 1H), 7.87 (d, J¼8.25 Hz, 2H),
(td, J¼7.85, 1.80 Hz, 1H), 7.53e7.56 (m, 1H), 7.30e7.34 (m, 1H),
7.18e7.20 (m, 1H), 3.08e3.13 (m, 2H), 2.62 (d, J¼1.29 Hz, 3H),
1.81e1.91 (m, 2H), 1.42e1.55 (m, 2H), 0.96 (t, J¼7.19 Hz, 3H); 13C
7.68e7.74 (td, J¼7.77, 1.70 Hz, 1H), 7.50 (d, J¼7.95 Hz, 1H), 7.34 (d,
J¼8.25 Hz, 2H), 7.25e7.29 (m, 2H), 2.59 (s, 3H), 2.43 (s, 3H); 13C
NMR (75 MHz, CDCl3)
d
155.8,149.6,149.3,144.2,139.0,136.8,129.9,
NMR (100 MHz, CDCl3) d 155.6, 151.4, 149.4, 137.0, 127.2, 124.4, 121.1,
127.4, 124.1, 121.0, 21.5, 15.0; IR (film, cmꢁ1): 3020, 1597, 1581, 1568,
1465, 1431, 1311, 1301, 1215, 1145, 1085; HRMS m/z calculated for
C14H13O2 [MþH]þ: 213.2887; found 213.2882.
55.7, 24.2, 21.7, 15.2, 13.5; IR (film, cmꢁ1): 2962, 1618, 1581, 1568,
1465, 1431, 1298, 1128; HRMS m/z calculated for C12H18NO2S
[MþH]þ: 240.1058; found 240.1053.
4.2.2. Compound 3b. This compound was prepared by the general
4.2.8. Compound 3h. This compound was prepared by the general
procedure and was obtained as
a
white solid. Yield¼67%.
procedure and was obtained as
a
white solid. Yield¼66%.
Mp¼65e66 ꢀC; Rf¼0.35 (EA/Hexane¼3:7). 1H NMR (300 MHz,
Mp¼75e77 ꢀC; Rf¼0.33 (EA/Hexane¼3:7). 1H NMR (400 MHz,
CDCl3)
d
8.57e8.60 (m, 2H), 7.77e7.80 (m, 2H), 7.69e7.74 (td,
CDCl3) d 8.55e8.56 (m, 2H), 7.88e7.98 (m, 4H), 7.58e7.71 (m, 3H),
J¼7.76, 1.7 Hz, 1H), 7.50e7.53 (m, 1H), 7.41e7.43 (m, 2H), 7.25e7.30
7.49 (d, J¼7.92 Hz, 1H), 7.37 (s, 1H), 7.23e7.26 (m, 1H), 2.63 (s, 3H);
(m, 2H), 2.60 (d, J¼1.23 Hz, 3H), 2.43 (s, 3H); 13C NMR (75 MHz,
13C NMR (100 MHz, CDCl3)
d
155.6, 150.2, 149.4, 138.7, 136.9, 135.1,
CDCl3)
d
155.7, 149.9, 149.4, 141.7, 139.5, 136.9, 134.1, 129.8, 129.1,
132.2, 129.6, 129.6, 129.4, 129.1, 128.8, 127.9, 127.6, 124.3, 122.4,
121.1, 15.1; IR (film, cmꢁ1): 3018, 1618, 1581, 1568, 1465, 1431, 1309,
1215, 1145, 1126, 1070; HRMS m/z calculated for C18H16NO2S
[MþH]þ: 310.0902; found 310.0896.
127.7, 124.5, 124.2, 121.1, 21.3, 15.1; IR (film, cmꢁ1): 3020, 1610, 1581,
1566, 1465, 1431, 1313, 1300, 1215, 1139, 1083; HRMS m/z calculated
for C15H16NO2S [MþH]þ: 274.0902; found 274.0901.
4.2.3. Compound 3c. This compound was prepared by the general
4.2.9. Compound 3i. This compound was prepared by the general
procedure and was obtained as
a
white solid. Yield¼61%.
procedure and was obtained as
a
white solid. Yield¼70%.
Mp¼50e51 ꢀC; Rf¼0.36 (EA/Hexane¼3:7). 1H NMR (400 MHz,
Mp¼98e100 ꢀC; Rf¼0.31 (EA/Hexane¼3:7). 1H NMR (300 MHz,
CDCl3)
d
8.55 (d, J¼4.52 Hz, 1H), 7.89 (d, J¼9.00 Hz, 2H), 7.70 (t,
CDCl3)
d
8.60e8.62 (m, 1H), 8.43 (s, 2H), 8.11 (s, 1H), 7.76 (td, J¼7.80,

4406
Y.-H. Xu et al. / Tetrahedron 69 (2013) 4403e4407
1.80 Hz, 1H), 7.55e7.58 (m, 1H), 7.30e7.37 (m, 2H), 2.66 (d,
(EA/Hexane¼2:3). 1H NMR (400 MHz, CDCl3)
d 9.47 (s, 1H),
J¼1.23 Hz, 3H); 13C NMR (75 MHz, CDCl3)
d
154.7,152.5,149.5,144.6,
8.61e8.35 (dd, J¼7.40, 1.08 Hz, 1H), 8.07 (d, J¼8.24 Hz, 1H), 7.90 (d,
137.1, 133. 4, 132.9, 127.8 (m), 127.6, 126.9 (m), 124.5 (d, J¼52.03 Hz),
120.9 (d, J¼60.46 Hz), 15.21; IR (film, cmꢁ1): 3018, 1612, 1581, 1568,
1433, 1359, 1330, 1313, 1280, 1215, 1186, 1149, 1107; HRMS m/z
calculated for C16H12NO2SF6 [MþH]þ: 396.0493; found 396.0493.
J¼7.84 Hz, 1H), 7.81e7.83 (m, 1H), 7.52e7.63 (m, 3H), 7.25e7.30 (s,
3H), 3.48 (s, 2H), 2.38 (s, 3H); 13C NMR (100 MHz, CDCl3)
d 168.4,
147.4, 142.3, 137.5, 135.7, 135.3, 134.2, 129.2, 128.9, 128.6, 128.6,
127.1, 126.9, 126.4, 124.4, 123.9, 123.5, 121.3, 36.5, 24.4; IR (film,
cmꢁ1): 3018, 1710, 1612, 1595, 1566, 1506, 1371, 1357, 1296, 1215,
1153, 1124, 1109; HRMS m/z calculated for C21H17NO3SNa [MþNa]þ:
386.0827; found 386.0828.
4.2.10. Compound 3j. This compound was prepared by the general
procedure and was obtained as
a
white solid. Yield¼59%.
Mp¼120e122 ꢀC; Rf¼0.35 (EA/Hexane¼3:7). 1H NMR (300 MHz,
CDCl3)
d
8.57e8.59 (m, 1H), 7.69e7.74 (td, J¼7.80, 1.93 Hz, 1H), 7.50
4.2.16. Compound 4c. This compound was prepared by the gen-
eral procedure except using Pd(CH3CN)2Cl2 as the catalyst and
was obtained as a white solid. Yield¼53%. Mp¼173e174 ꢀC;
(d, J¼7.95 Hz,1H), 7.32e7.34 (m,1H), 7.24e7.29 (m,1H), 6.94 (s, 2H),
2.69 (s, 3H), 2.49 (d, J¼1.23 Hz, 3H), 2.29 (s, 3H); 13C NMR (75 MHz,
CDCl3)
d
155.8, 149.4, 147.9, 142.9, 139.4, 136.9, 135.5, 132.1, 131.9,
Rf¼0.33 (EA/Hexane¼2:3). 1H NMR (300 MHz, CDCl3)
d 9.42 (s,
124.1, 120.9, 22.6, 21.0, 14.9; IR (film, cmꢁ1): 3018, 1602, 1581, 1566,
1465, 1431, 1301, 1215, 1134, 1053; HRMS m/z calculated for
C17H20NO2S [MþH]þ: 302.1215 Found 302.1218.
1H), 7.83e7.86 (m, 1H), 7.80e7.82 (m, 1H), 7.77e7.79 (m, 1H),
7.30e7.35 (m, 5H), 3.57 (s, 2H), 2.41 (s, 3H), 2.35 (s, 3H); 13C NMR
(75 MHz, CDCl3)
d 168.3, 146.8, 144.7, 142.4, 138.2, 137.5, 130.0,
128.8, 126.9, 126.5, 123.9, 121.4, 36.2, 24.4, 21.5; IR (film, cmꢁ1):
3018, 1708, 1612, 1597, 1568, 1371, 1359, 1298, 1215, 1145, 1076;
HRMS m/z calculated for C18H17NO3SNa [MþNa]þ: 350.0827;
found 350.0826.
4.2.11. Compound 3k. This compound was prepared by the general
procedure and was obtained as
a
white solid. Yield¼65%.
Mp¼67e69 ꢀC; Rf¼0.32 (EA/Hexane¼3:7). 1H NMR (400 MHz,
CDCl3)
d
8.55e8.59 (m, 1H), 8.12 (d, J¼8.16 Hz, 2H), 7.81 (d,
J¼8.16 Hz, 2H), 7.73 (t, J¼8.60 Hz, 1H), 7.52 (d, J¼7.92 Hz, 1H),
4.2.17. Compound 4d. This compound was prepared by the gen-
eral procedure except using Pd(CH3CN)2Cl2 as the catalyst and
was obtained as a white solid. Yield¼68%. Mp¼165e167 ꢀC;
7.25e7.32 (m, 2H), 2.61 (s, 3H); 13C NMR (100 MHz, CDCl3)
d
155.2,
151.5,149.5,145.4,137.0,134.9 (q, J¼33.07 Hz),128.6,128.0,126.4 (q,
J¼3.39 Hz), 124.5 (d, J¼9.07 Hz), 121.5 (d, J¼59.06 Hz), 15.1; IR (film,
cmꢁ1): 3024, 1606, 1581, 1566, 1465, 1433, 1404, 1321, 1215, 1172,
1149, 1085, 1062, 1016; HRMS m/z calculated for C15H13NO2SF3
[MþH]þ: 328.0619; found 328.0618.
Rf¼0.35 (EA/Hexane¼2:3). 1H NMR (400 MHz, CDCl3)
d 9.37 (s,
1H), 7.79e7.81 (m, 3H), 7.31e7.33 (m, 3H), 6.94e6.96 (m, 2H), 3.81
(s, 3H), 3.53 (s, 2H), 2.31 (s, 3H); 13C NMR (100 MHz, CDCl3)
d
168.4, 163.7, 146.2, 142.3, 137.5, 132.6, 129.2, 128.8, 126.9, 126.4,
123.9, 122.0, 114.7, 55.7, 36.2, 24.4; IR (film, cmꢁ1): 3018, 1708,
1612, 1595, 1568, 1496, 1371, 1359, 1294, 1261, 1215, 1143, 1118;
HRMS m/z calculated for C18H17NO4SNa [MþNa]þ: 366.0776;
found 366.0779.
4.2.12. Compound 3l. This compound was prepared by the general
procedure and was obtained as
a
white solid. Yield¼61%.
Mp¼122e124 ꢀC; Rf¼0.28 (EA/Hexane¼3:7). 1H NMR (300 MHz,
CDCl3)
d
8.61e8.63 (m, 1H), 7.72e7.78 (td, J¼7.77, 1.80 Hz, 1H),
7.53e7.56 (m,1H), 7.50e7.52 (m,1H), 7.47 (s, 2H), 7.29e7.33 (m,1H),
4.2.18. Compound 4e. This compound was prepared by the general
procedure except using Pd(CH3CN)2Cl2 as the catalyst and was
obtained as a white solid. Yield¼49%. Mp¼166e167 ꢀC; Rf¼0.30
2.51 (d, J¼1.20 Hz, 3H); 13C NMR (75 MHz, CDCl3)
d 155.2,151.7,149.6,
138.9, 137.0, 136.5, 135.2, 131.3, 130.1, 124.6, 121.2, 15.4; IR (film,
cmꢁ1): 3020, 1581, 1562, 1537, 1431, 1363, 1328, 1215, 1159, 1136;
HRMS m/z calculated for C14H11NO2SCl3 [MþH]þ: 361.9576; found
361.9579.
(EA/Hexane¼2:3). 1H NMR (400 MHz, CDCl3)
d 9.08 (s, 1H),
8.20e8.24 (m, 1H), 7.89e7.93 (m, 1H), 7.73e7.79 (m, 3H), 7.32e7.36
(m, 3H), 3.62 (s, 2H), 2.34 (s, 3H); 13C NMR (100 MHz, CDCl3)
d 169.1,
152.9, 133.4, 133.0, 131.5, 128.4, 128.4, 127.6, 126.6, 126.5, 124.0,
122.6, 102.7, 21.0; IR (film, cmꢁ1): 2945, 2833, 1654,1448,1417, 1217,
1112, 1029; HRMS m/z calculated for C17H14N2O5SNa [MþNa]þ:
381.0521 Found 381.0519.
4.2.13. Compound 3m. This compound was prepared by the gen-
eral procedure and was obtained as a white solid. Yield¼59%.
Mp¼97e99 ꢀC; Rf¼0.30 (EA/Hexane¼3:7). 1H NMR (400 MHz,
CDCl3)
d
8.56e8.61 (m, 1H), 7.90 (d, J¼8.40 Hz, 2H), 7.68e7.74 (m,
3H), 7.51 (d, J¼7.92 Hz,1H), 7.25e7.30 (m, 2H), 2.59 (s, 3H); 13C NMR
4.2.19. Compound 4f. This compound was prepared by the general
procedure except using Pd(CH3CN)2Cl2 as the catalyst and was
obtained as a white solid. Yield¼53%. Mp¼187e189 ꢀC; Rf¼0.30
(100 MHz, CDCl3)
d 169.1, 152.9, 133.4, 133.0, 131.5, 128.4, 128.4,
127.6, 126.6, 126.5, 124.0, 122.6, 102.7, 21.0; IR (film, cmꢁ1): 3018,
1612,1581,1568,1467,1431,1384,1315,1215,1147,1082,1055,1006;
HRMS m/z calculated for C14H13NO2SI [MþH]þ: 385.9712; found
385.9716.
(EA/Hexane¼2:3). 1H NMR (400 MHz, CDCl3)
d 9.34 (s, 1H), 7.74 (d,
J¼8.08 Hz, 2H), 7.61 (s,1H), 7.28 (d, J¼8.08 Hz, 2H), 7.21 (d, J¼9.0 Hz,
1H), 7.12 (d, J¼7.72 Hz, 1H), 3.49 (s, 2H), 2.38 (s, 3H), 2.35 (s, 3H),
2.32 (s, 3H); 13C NMR (75 MHz, CDCl3)
d 168.4, 146.8, 144.6, 139.6,
4.2.14. Compound 4a. This compound was prepared by the gen-
eral procedure and was obtained as a white solid. Yield¼57%.
Mp¼61e63 ꢀC; Rf¼0.35 (EA/Hexane¼3:7). 1H NMR (300 MHz,
138.2, 137.6, 136.7, 130.0, 129.9, 126.9, 126.6, 123.6, 121.7, 35.8, 24.4,
21.5, 21.5; IR (film, cmꢁ1): 2252, 1707, 1595, 1571, 1350, 1298, 1215,
1141; HRMS m/z calculated for C19H19NO3SNa [MþNa]þ: 364.0983
Found 364.0983.
CDCl3)
d
8.41 (d, J¼4.89 Hz, 1H), 7.84 (d, J¼8.22 Hz, 2H), 7.33 (s,
1H), 7.30 (s, 2H), 7.21 (m, 1H), 7.07 (d, J¼4.77 Hz, 1H), 2.57 (s, 3H),
2.41 (s, 3H), 2.35 (s, 3H); 13C NMR (75 MHz, CDCl3)
d
155.8, 150.0,
4.2.20. Compound 4g. This compound was prepared by the gen-
eral procedure except using Pd(CH3CN)2Cl2 as the catalyst and was
obtained as a white solid. Yield¼63%. Mp¼157e159 ꢀC; Rf¼0.30
149.1, 148.1, 144.2, 139.1, 129.8, 127.4, 125.1, 122.1, 21.5, 21.1, 15.1; IR
(film, cmꢁ1): 3020, 1597, 1444, 1379, 1311, 1301, 1215, 1145, 1085;
HRMS m/z calculated for C16H18NO2S [MþH]þ: 288.1058; found
288.1056.
(EA/Hexane¼2:3). 1H NMR (400 MHz, CDCl3)
d 9.41 (s, 1H), 7.74 (d,
J¼8.08 Hz, 2H), 7.38e7.39 (m, 1H), 7.28 (d, J¼8.08 Hz, 1H), 7.20 (d,
J¼8.32 Hz, 1H), 6.87e6.90 (m, 1H), 3.78 (s, 3H), 3.47 (s, 2H), 2.38 (s,
4.2.15. Compound 4b. This compound was prepared by the general
procedure except using Pd(CH3CN)2Cl2 as the catalyst and was
obtained as a white solid. Yield¼61%. Mp¼188e189 ꢀC; Rf¼0.31
3H), 2.32 (s, 3H); 13C NMR (100 MHz, CDCl3)
d 168.4, 158.8, 146.7,
144.7, 138.6, 138.1, 134.8, 130.1, 126.9, 124.4, 122.4, 116.8, 110.5,
55.6, 35.5, 24.5, 21.6; IR (film, cmꢁ1): 3018, 2945, 2835, 1708, 1595,

Y.-H. Xu et al. / Tetrahedron 69 (2013) 4403e4407
4407
T.; Hata, N.; Fujiwara, H.; Ban, Y. J. Org. Chem. 1982, 47, 4713e4717; (d) Simpkins,
N. S. Sulphones in Organic Synthesis; Pergamon: Oxford, United Kingdom, 1993.
3. (a) Narasaka, K.; Mochizuki, T.; Hayakawa, S. Chem. Lett. 1994, 1705e1708; (b)
Mochizuki, T.; Hayakawa, S.; Narasaka, K. Bull. Chem. Soc. Jpn. 1996, 69,
2317e2325 and references cited therein.
1571, 1474, 1350, 1288, 1215, 1026; HRMS m/z calculated for
C19H19NO4SNa [MþNa]þ: 380.0932 Found 380.0939.
4.2.21. Compound 4h. This compound was prepared by the general
procedure except using Pd(CH3CN)2Cl2 as the catalyst and was
obtained as a white solid. Yield¼40%. Mp¼204e206 ꢀC; Rf¼0.30
4. Kharasch, M. S.; Mosher, R. A. J. Org. Chem. 1952, 17, 453e456.
5. (a) Liu, L. K.; Chi, Y.; Jen, K.-Y. J. Org. Chem. 1980, 45, 406e410; (b) Kamigata, N.;
Sawada, H.; Suzuki, N.; Kobayashi, M. J. Org. Chem. 1983, 48, 3793e3796; (c)
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6. Truce, W. E.; Wolf, G. C. J. Org. Chem. 1971, 36, 1727e1732.
(EA/Hexane¼2:3). 1H NMR (300 MHz, CDCl3)
d 9.42 (s, 1H), 7.82 (d,
J¼8.08 Hz, 2H), 7.81 (s, 1H), 7.50 (d, J¼7.88 Hz, 1H), 7.36 (d,
7. Bandgar, B. P.; Bettigeri, S. V.; Phopase, J. Org. Lett. 2004, 6, 2105e2108.
8. (a) Zhao, X. D.; Dimitrijevic, E.; Dong, V. M. J. Am. Chem. Soc. 2009, 131,
3466e3467; (b) Zhao, X.; Dong, V. M. Angew. Chem., Int. Ed. 2010, 49, 932e934.
9. (a) Pankajakshan, S.; Xu, Y. H.; Cheng, J. K.; Low, M. T.; Loh, T. P. Angew.
Chem., Int. Ed. 2012, 51, 5701e5705; (b) Zhu, M. K.; Zhao, J. F.; Loh, T. P. Org.
Lett. 2011, 13, 6308e6311; (c) Feng, C.; Loh, T. P. Chem. Commun. 2011, 47,
10458e10460; (d) Xu, Y. H.; Chok, Y. K.; Loh, T. P. Chem. Sci. 2011, 2,
1822e1825; (e) Xu, Y. H.; Wang, W. J.; Wen, Z. K.; Hartley, J. J.; Loh, T. P.
Tetrahedron Lett. 2010, 51, 3504e3507; (f) Zhu, M. K.; Zhao, J. F.; Loh, T. P. J.
Am. Chem. Soc. 2010, 132, 6284e6285; (g) Zhou, H.; Xu, Y. H.; Chang, W. J.;
Loh, T. P. Angew. Chem., Int. Ed. 2009, 48, 5355e5357; (h) Zhou, H.; Chung,
W. J.; Xu, Y. H.; Loh, T. P. Chem. Commun. 2009, 3472e3474; (i) Xu, Y. H.; Lu,
J.; Loh, T. P. J. Am. Chem. Soc. 2009, 131, 1372e1373; For metal-catalyzed
direct alkenyl CeH bond functionalization also see: Hatamoto, Y.; Saka-
guchi, S.; Ishii, Y. Org. Lett. 2004, 6 4623 Ge, H.; Niphakis, M. J.; Georg, G. I. J.
Am. Chem. Soc. 2008, 130, 3708e3709; Giri, R.; Yu, J.-Q. J. Am. Chem. Soc.
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Mochida, S.; Hirano, K.; Satoh, T.; Miura, M. J. Org. Chem. 2009, 74,
6295e6298; Li, M.; Li, L.; Ge, H. Adv. Synth. Catal. 2010, 352, 2445e2449; Ho,
C.-Y.; He, L. Angew. Chem., Int. Ed. 2010, 49, 9182e9186; Yu, H.; Jin, W.; Sun,
C.; Chen, J.; Du, W.; He, S.; Yu, Z. Angew. Chem., Int. Ed. 2010, 49, 5792e5797;
Hu, P.; Huang, S.; Xu, J.; Shi, Z.-J.; Su, W. Angew. Chem., Int. Ed. 2011, 50,
9926e9930; Yeung, C. S.; Dong, V. M. Chem. Rev. 2011, 111, 1215e1292;
Besset, T.; Kuhl, N.; Paturean, F. W.; Glorious, F. Chem.dEur. J. 2011, 17 7167;
Li, C.; Zhang, Y.; Li, P.; Wang, L. J. Org. Chem. 2011, 76, 4692e4696; Bai, Y.;
Zeng, J.; Cai, S.; Liu, X.-W. Org. Lett. 2011, 13, 4394e4397; Bi, L.; Georg, G. I.
Org. Lett. 2011, 13, 5413e5415; Yu, Y.-Y.; Niphakis, M. J.; Georg, G. I. Org. Lett.
2011, 13, 5932e5935; Shi, Z.; Zhang, C.; Tang, C.; Jiao, N. Chem. Soc. Rev. 2011,
41, 3381e3430; Liwosz, T. W.; Chemler, S. R. J. Am. Chem. Soc. 2012, 134,
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J¼8.08 Hz, 2H), 7.23e7.28 (m, 1H), 3.55 (s, 2H), 2.45 (s, 3H), 2.37 (s,
3H); 13C NMR (75 MHz, CDCl3)
d 168.3, 146.0, 145.0, 142.3, 138.9,
137.7, 131.8, 130.2, 128.7, 127.0, 125.6, 122.3, 118.6, 37.7, 24.3, 21.6; IR
(film, cmꢁ1): 3018, 2399, 1712, 1606, 1589, 1475, 1371, 1357, 1215,
1141; HRMS m/z calculated for C18H16NO3SBrNa [MþNa]þ:
427.9932 Found 427.9931.
4.2.22. Compound 4i. This compound was prepared by the general
procedure except using Pd(CH3CN)2Cl2 as the catalyst and was
obtained as a white solid. Yield¼33%. Mp¼172e174 ꢀC; Rf¼0.31 (EA/
Hexane¼3:2). 1H NMR (300 MHz, CDCl3)
d 8.88 (s, 1H), 7.77 (d,
J¼8.08 Hz, 2H), 7.30e7.35 (m, 2H), 7.26 (d, J¼8.08 Hz, 2H),
6.93e6.99 (m, 1H), 6.87 (d, J¼7.43 Hz, 1H), 4.84 (s, 2H), 2.43 (s, 3H),
2.21 (s, 3H); 13C NMR (75 MHz, CDCl3)
d 188.7, 156.0, 145.3, 139.9,
137.6, 132.8, 130.2, 127.3, 126.9, 121.7, 118.7, 117.1, 63.7, 24.1, 21.6; IR
(film, cmꢁ1): 3018, 1670, 1618, 1477, 1369, 1301, 1215, 1138, 1016;
HRMS m/z calculated for C18H17NO4SNa [MþNa]þ: 366.0776; found
366.0780.
Acknowledgements
We gratefully acknowledge the Nanyang Technological Univer-
sity and the Singapore Ministry of Education Academic Research
Fund Tier 2 (No. T206B1221; T207B1220RS) for the financial sup-
port of this research. We also thank the financial support of Uni-
versity Science and Technology of China.
10. High-valent Pd species with CeS bond please see: (a) Reference 8b. (b) Canty,
A. J.; Jin, H.; Skelton, B. W.; White, A. H. Inorg. Chem. 1998, 37, 3975e3981; (c)
Canty, A. J.; Jin, H. J. Organomet. Chem. 1998, 565, 135e142.
References and notes
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Trost, B. M.; Chan, D. M. T. J. Am. Chem. Soc. 1982, 104, 3733e3735; (c) Ohnuma,
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