Regio- and stereoselective synthesis of (Z)-2-Arylsulfanyl allylic alcohols using anhydrous CeCl3 as catalyst under solvent free conditions

Article abstract of DOI:10.1016/j.tetlet.2013.07.142

Anhydrous CeCl₃ was successfully employed as catalyst for the synthesis of (Z)-2-Arylsulfanyl allylic alcohols from propargylic alcohols and thiols under solvent free conditions. The products were obtained in good to excellent yields.

Full text of DOI:10.1016/j.tetlet.2013.07.142

Tetrahedron Letters xxx (2013) xxx–xxx
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Tetrahedron Letters
journal homepage: www.elsevier.com/locate/tetlet
Regio- and stereoselective synthesis of (Z)-2-Arylsulfanyl allylic
alcohols using anhydrous CeCl3 as catalyst under solvent free
conditions
a
b
Claudio C. Silveira a, , Guilherme M. Martins , Samuel R. Mendes
⇑
a Departamento de Química, Universidade Federal de Santa Maria, 97105-900 Santa Maria, RS, Brazil
b GAPAM–Departamento de Química, Universidade do Estado de Santa Catarina, 89219-710 Joinville, SC, Brazil
a r t i c l e i n f o
a b s t r a c t
Article history:
Anhydrous CeCl3 was successfully employed as catalyst for the synthesis of (Z)-2-Arylsulfanyl allylic alco-
hols from propargylic alcohols and thiols under solvent free conditions. The products were obtained in
good to excellent yields.
Received 14 May 2013
Revised 25 July 2013
Accepted 27 July 2013
Available online xxxx
Ó 2013 Elsevier Ltd. All rights reserved.
Keywords:
Click chemistry
Solvent free
Propargylic alcohols
Thiols
Cerium(III) chloride
Click chemistry is a concept introduced in 2001 by Sharpless1 to
describe reactions capable of connecting two molecules with high
yields, under simple reaction conditions. To be characterized as
click chemistry the reaction must be rapid, stereospecific, and gen-
erate inoffensive by-products. Furthermore, it must be performed
without solvents or in nontoxic solvents, using stable starting
materials and of simple production.
In recent years, the number of publications involving the use of
click reaction for the preparation of new molecules has grown
exponentially. Many researchers reported this application for the
synthesis of polymers,2 N,N’-disubstituted thioureas,3 copper-cata-
lyzed azide-alkyne cycloaddition (CuAAC),4 and many others.5 The
thiol-clock chemistry has been the subject of a recently published
detailed review article.6 The thiol addition is also a very useful
reaction in material chemistry.6,7
Allylic alcohols are important intermediates in organic synthe-
sis such as for cyclopropanation reactions8 and allylic substitu-
tion;9 they can be isomerized into carbonyl compounds in the
presence of a transition metal catalyst.10 They are also very impor-
tant in the synthesis of natural products and pharmaceuticals.11
The synthesis of allylic alcohols containing metals or heteroatoms
is also of considerable interest for organic synthesis,12 as they pro-
vide a useful intermediate for change through the introduction and
removal of the metal or heteroatom.13 Substituted allylic alcohols
are generally prepared by a Reformatsky reaction14 of the corre-
sponding ketones or by the Horner–Wadsworth–Emmons reac-
tion,15 but a mixture of isomers has been usually obtained.
Organochalcogen compounds play an important role in modern
organic synthesis in view of their chemo, regio, and stereoselective
reactions16 and their useful biological activities.17 Among the dif-
ferent classes of organochalcogen compounds, vinylic chalcoge-
nides constitute
a very useful group and have attracted
considerable attention in recent years as synthetic precursors.18 Vi-
nyl sulfides are particularly interesting, serving as intermediaries
for various organic transformations.19 The most common method
to prepare vinyl sulfides involves the addition of thiols or its an-
ions, to terminal or internal alkynes, usually by metal-catalyzed
reactions.20 From the various classes of alkynes, propargylic alco-
hols are particularly interesting since the sulfanyl allylic alcohols,
resulting from the corresponding thiol addition, can be functional-
ized in many ways.21 Another very important alternative for the
preparation of vinyl sulfides is the metal-catalyzed reaction of thi-
ols with vinyl halides.22
On the other hand, lanthanide salts have been shown to be
excellent catalysts, widely used as Lewis acids. Many of these salts
have attracted great interest in organic syntheses due to their ease
of handling, low toxicity, high resistance to water, and stability.23
In this context, there has been a series of articles reporting the
use of CeCl3 as catalyst.24 CeCl3 has been used in different ways,
as heptahydrate, anhydrous, and in combination with NaI.25 Due
⇑
Corresponding author. Fax: +55 55 32208754.
E-mail addresses: silveira@quimica.ufsm.br (C.C. Silveira), samuel.mendes@
udesc.br (S.R. Mendes).
0040-4039/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tetlet.2013.07.142
Please cite this article in press as: Silveira, C. C.; et al. Tetrahedron Lett. (2013), http://dx.doi.org/10.1016/j.tetlet.2013.07.142

2
C. C. Silveira et al. / Tetrahedron Letters xxx (2013) xxx–xxx
Table 1
to our interest in developing new methods and new applications of
Optimization of conversion 1a–3aa
salts of cerium(III) in organic synthesis, we decided to study the
reaction of propargylic alcohols with thiols using a cerium(III) salt
as catalyst. We observed previously that cerium salts are efficient
acid catalysts, capable of promoting several reactions with high re-
gio and stereoselectivity.26,24c Therefore, the main goal was in
obtaining a regio- and stereoselective addition, since most of the
described methods of thiol addition to alkynes give rise to mix-
tures of regio- and/or stereoisomers.
In preliminary experiments, the best reaction conditions were
pursued by the use of benzenethiol (1a, 1.1 mmol) and 2,4-diphe-
nylbut-3-yn-2-ol (2a, 1.0 mmol) as starting materials (Table 1).
First, the solvent effect was tested using MeNO2, MeCN, and i-pro-
panol under solvent-free conditions (entries 1–4). The results re-
vealed that the best yields were obtained under solvent-free
Entry
Solvent
Catalyst (equiv)
Time (h)
Yieldb (%)
86
1
2
3
4
5
6
7
8
—
CeCl3 (0.3)
0.5
6
6
6
6
0.5
0.5
0.5
c
MeNO2
CeCl3 (0.3)
—
—
—
c
MeCN
CeCl3 (0.3)
c
i-propanol
CeCl3 (0.3)
—
—
—
—
CeCl3Á7H2O (0.3)
Ce(OTf)3 (0.3)
Ce(NO3)3Á6H2O (0.3)
CeCl3 (0.2)
30
45
50
86
a
Reaction conditions: benzenethiol (1a, 1.1 mmol), 2,4-diphenylbut-3-yn-2-ol
(2a, 1.0 mmol), at 80 °C.
Isolated yields.
No reaction.
b
c
R1
R4
R1
S
S
SH
OH
CeCl3 (20 mol%)
R4
HO
HO
+
R4
+
R2
R1
R3
R3
R3
2a-g
Solvent free, 80 °C
R2
R2
3a-l (Z:E)
1a-d
R
1 = H, Cl, MeO; R2 = Ph, p-ClPh, Me; R3 = H, Ph, Me; R4 = Ph, C4H9; R2 = R3 = C5H10
Scheme 1.
Table 2
Synthesis of (Z)-2-Arylsulfanyl allylic alcohols using anhydrous CeCl3 as catalysta
Entry
Thiol
Propargylic alcohol
Productc
Time (h)
Ratio Z:E
Yieldd (%)
SH
HO
S
1a
CH3
1
0.5
98:2
86
2a
HO
CH3
S
3a
SH
Cl
1b
Cl
2
3
2a
2a
0.5
96:4
98:2
53
91
HO
CH3
S
3b
SH
O
H3C
H C
3
O
0.25
1c
HO
CH3
3c
HO
S
CH3
Cl
HO
2b
4
1a
0.5
100:0
95
CH3
3d
Cl
O
H3C
S
HO
5
1c
2b
0.25
100:0
80
CH3
3e
Cl
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C. C. Silveira et al. / Tetrahedron Letters xxx (2013) xxx–xxx
3
Table 2 (continued)
Entry
Thiol
Propargylic alcohol
HO
Productc
Time (h)
1.25
Ratio Z:E
Yieldd (%)
S
6
1a
55:45
86
2c
HO
3f
HO
S
S
7
8
1a
1a
0.5
0.5
100:0
100:0
84
81
2d
HO
HO
3g
HO
H3C
CH3
2e
3h
CH3
H3C
HO
S
2f
9
1a
1a
0.5
3.5
100:0
94:6
75
65
HO
3i
C4H9
HO
CH3
S
C4H9
10
HO
2g
CH3
3j
C2H5S
11
12
C2H5SH 1d
2a
2e
1.5
3.0
—
—
50b
42b
CH3
3k
C2H5S
H3C
1d
CH3
3l
a
b
c
Reaction performed at 80 °C, using anhydrous CeCl3 (20 mol %) under solvent free.
MeNO2 (2 mL) was used as solvent.
Product was detected by 1H NMR, 13C NMR, and GC–MS.
Isolated yields.
d
Reactions of propargyl alcohols with various thiols were per-
formed. The corresponding products resulting from addition to
the triple bond were obtained from aromatic compounds such as
benzenethiol, 4-chlorobenzenethiol, and 4-methoxy benzenethiol.
Surprisingly, however, when the reaction was carried out using
ethanethiol, under the standard conditions, no reaction was ob-
served. When MeNO2 was employed as solvent and under these
conditions, the nucleophilic substitution reaction wasobserved,
furnishing the corresponding propargylic thiol, albeit in low yields
(entries 11 and 12). Catalysts for the OH/SR substitution on prop-
argylic alcohols include PTSA,28 Ru,29 Au,30 and FeCl3.31 When
employing arylthiols carrying electron withdrawing groups, such
as 4-chlorobenzenethiol, the yield decrease considerably to 53%
(entry 2). Using an electron releasing group, as 4-methoxyben-
zenethiol, the yield increased from 86% to 91%, and the reaction
time was reduced by half (Table 2, entry 3). The reaction with aro-
matic thiols proved to be regio- and stereoselective, as determined
by 1H NMR, 13C NMR, and GC/MS, with a very high preference for
the formation of the Z isomers, with the exception of alcohol 2c
(entry 6). A NOESY experiment on the major isomer of 3e (Fig. 1)
exhibited a clear coupling between the vinyl hydrogen d 7.29 (s,
1H) with the methyl hydrogens d 1.81 (s, 3H); revealing its geom-
etry as Z. A similar pattern was observed for compound 3j. The
S
C4H9
H
MeO
S
HO
HO
H
CH3
CH3
3e
3j
Cl
Figure 1. Results of the NOESY studies.
conditions. The type of catalyst and its amountwere also evaluated
using anhydrous CeCl3, Ce(OTf)3, CeCl3Á7H2O, and Ce(NO3)3Á6H2O
(entries 5–8). The best yield was obtained by the use of anhydrous
CeCl3 (0.2 equiv, entry 8). Next, the amount of CeCl3 was checked;
it was observed a decrease in the yields when 0.1 equiv was used,
while the use of 0.3 equiv did not increase significantly the perfor-
mance. The temperature was also evaluated. The best results were
obtained at 80 °C (entry 8), yields were lower at 50 °C, while at
room temperature only traces of the product were observed. On
the other hand, at 100 °C there was a complete lack of selectivity,
with a formation of Z/E mixtures.
In order to explore the scope and limitations of the method, the
transformation of Scheme 1 was extended to other examples, un-
der the optimized conditions (Table 2).27
Please cite this article in press as: Silveira, C. C.; et al. Tetrahedron Lett. (2013), http://dx.doi.org/10.1016/j.tetlet.2013.07.142

4
C. C. Silveira et al. / Tetrahedron Letters xxx (2013) xxx–xxx
20. (a) Riduan, S. N.; Ying, J. Y.; Zhang, Y. Org. Lett. 2012, 14, 1780; (b) Malyshev, D.
A.; Scott, N. M.; Marion, N.; Steven, E. D.; Ananikov, V. P.; Beletskaya, I. P.; Nola,
S. P. Organometallics 2006, 25, 4462; (c) Yamashita, F.; Kuniyasu, H.; Terao, J.;
Kambe, N. Org. Lett. 2008, 10, 101; (d) Cao, C.; Fraser, L. R.; Love, J. A. J. Am.
Chem. Soc. 2005, 127, 17614; (e) Ananikov, V. A.; Orlov, N. V.; Beletskaya, I. P.
Organometallics 2007, 26, 740; (f) Kondo, A. K.; Takami, K.; Yorimitsu, H.;
Oshima, K. J. Org. Chem. 2005, 70, 6468; (g) Trofimov, B. A. Curr. Org.Chem. 2002,
6, 1121; (h) Ogawa, A.; Ikeda, T.; Kimura, K.; Hirao, T. J. Am. Chem. Soc. 1999,
121, 5108; (i) Manarin, F.; Roehrs, J. A.; Progol, M.; Alves, D.; Nogueira, C. W.;
Zeni, G. Tetrahedron Lett. 2007, 48, 4805; (j) Corma, A.; González-Arellano, C.;
Iglesias, M.; Sánchez, F. Appl. Catal., A 2010, 375, 49.
21. (a) Waters, M. S.; Cowen, J. A.; McWilliams, J. C.; Maligres, P. E.; Askin, D.
Tetrahedron Lett. 2000, 41, 141; (b) Ananikov, V. P.; Orlov, N. V.; Beletskaya, I. P.
Organometallics 2006, 25, 1970; (c) Xu, Y.; Hao, W.; Wang, D.; Cai, M. Heteroat.
Chem. 2008, 19, 639; (d) Arcadi, A.; Alfonsi, M.; Marinelli, F. Tetrahedron Lett.
2009, 50, 2060; (e) Jin, Z.; Xu, B.; Hammond, G. B. Eur. J. Org. Chem. 2010, 168;
(f) Biswas, S.; Samec, S. M. Chem.Commun. 2012, 48, 6586.
stereochemistry of the other examples was assigned from these
examples.
In summary, we have developed a simple and efficient method
for the stereoselective synthesis of (Z)-2-Arylsulfanyl allylic alco-
hols using anhydrous CeCl3 as catalyst, by addition of thiols into
propargyl alcohols under solvent-free conditions. Thereaction
showed excellent stereoselectivity leading to isomers of Z configu-
ration for most of the compounds. The products were obtained in
good yields and in short reaction times.
Acknowledgments
The authors thank FAPERGS (1014315/2010), CAPES and MCTI/
CNPq for financial support.
22. (a) Kao, H. L.; Lee, C. F. Org. Lett. 2011, 13, 5204; (b) Lin, Y. Y.; Wang, Y. J.; Lin, C.
H.; Cheng, J. H.; Lee, C. F. J. Org. Chem. 2012, 77, 6100. and references therein..
23. Bartoli, G.; De Nino, A.; Dalpozzo, R.; Maiuolo, L.; Nardi, M.; Procopio, A.;
Tagarelli, A. Lett. Org.Chem. 2005, 2, 51.
References and notes
24. (a) Tsuruta, H.; Yamaguchi, K.; Imamoto, T. Tetrahedron Lett. 2003, 59, 10419;
(b) Bartoli, G.; Dalpozzo, R.; DeNino, A.; Maiuo-lo, L.; Nardi, M.; Procopio, A.;
Tagarelli, A. Eur. J. Org. Chem. 2004, 2176; (c) Silveira, C. C.; Mendes, S. R.; Wolf,
L.; Martins, G. M. Tetrahedron Lett. 2010, 51, 2014; (d) Bartoli, G.; Marcantoni,
E.; Marcolini, M.; Sambri, L. Chem. Rev. 2010, 110, 6104.
25. (a) Sabitha, G.; Yadav, J. S. In Encyclopedia of Reagents for Organic Synthesis;
Paquette, L. A., Ed.; Wiley-VCH: Weinheim, 2006; (b) Bartoli, G.; DiAntonio, G.;
Giovannini, R.; Giuli, S.; Lanari, S.; Paoletti, M.; Marcantoni, E. J. Org. Chem.
2008, 73, 1919; (c) Yadav, J. S.; SubbaReddy, B. V.; Suresh Reddy, Ch.; Krishna,
A. D. Tetrahedron Lett. 2007, 48, 2029; (d) Meng, Q.; Sun, Y.; Ratovelomanana-
Vidal, V.; Genêt, J. P.; Zhang, Z. J. Org. Chem. 2008, 73, 3842; Cerium chloride
was dried accordingto: (e) Dimitrov, V.; Kostova, K.; Genov, M. Tetrahedron Lett.
1996, 37, 6787.
1. Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew. Chem., Int. Ed. 2001, 40, 2004.
2. (a) Brady, S. E.; Tyler, D. R. J. Inorg. Organomet. Polym. 2013, 23, 158; (b) Gunay,
U. S.; Durmaz, H.; Gungor, E.; Dag, A.; Hizal, G.; Tunca, U. J. Polym. Sci., Part
A:Polym. Chem. 2012, 50, 729; (c) Brändle, A.; Khan, A. Polym. Chem. 2012, 3,
3224.
ˇ ˇ
3. Štrukil, V.; Margetic´, D.; Igrc, M. D.; Eckert-Maksic´, M.; Frišcic, T. Chem.
Commun. 2012, 9705.
4. (a) Zarei, A.; Khazdooz, L.; Hajipour, A. R.; Aghaei, H.; Azizi, G. Synthesis 2012,
44, 3353; (b) Rostovtsev, V. V.; Green, L. G.; Fokin, V. V.; Sharpless, K. B. Angew.
Chem., Int. Ed. 2002, 41, 2596.
5. (a) Meldal, M. Macromol. Rapid Commun. 2008, 29, 1016; (b) Fahrenbach, A. C.;
Stoddart, J. F. Chem. AsianJ. 2011, 6, 2660.
26. (a) Silveira, C. C.; Mendes, S. R. Tetrahedron Lett. 2007, 48, 7469; (b) Silveira, C.
C.; Mendes, S. R.; Líbero, F. Synlett 2010, 5, 790; (c) Silveira, C. C.; Mendes, S. R.;
Wolf, L.; Martins, G. M. Tetrahedron Lett. 2010, 51, 4560; (d) Silveira, C. C.;
Mendes, S. R.; Martins, G. M. Tetrahedron Lett. 2012, 53, 1567; (e) Silveira, C. C.;
Mendes, S. R.; Villetti, M. A.; Back, D. F.; Kaufman, T. S. Green Chem. 2012, 14,
2912. and references therein..
6. Hoyle, C. E.; Lowe, A. B.; Bowman, C. N. Chem. Soc. Rev. 2010, 39, 1355.
7. (a) Yang, M.; Mao, J.; Nie, W.; Dong, Z.; Wang, D.; Zhao, Z.; Ji, X. J. Polym. Sci.,
Part A: Polym.Chem. 2012, 50, 2075; (b) Shen, Y.; Ma, Y.; Li, Z. J. Polym. Sci., Part
A: Polym. Chem. 2013, 51, 708.
8. Hoveyda, A. H.; Evans, D. A.; Fu, G. C. Chem. Rev. 1993, 93, 1307.
9. Alexakis, A.; Bäckvall, J. E.; Krause, N.; Pàmies, O.; Diéguez, M. Chem. Rev. 2008,
108, 2796.
27. Typical procedure: To
a mixture of propargylic alcohol (1.0 mmol) and
anhydrous CeCl3 (0.049 g, 20 mol %), was added the thiol (1.1 mmol). The
reaction progress was followed by GC–MS, the reaction mixture was stirred at
80 °C in an oil bath for the time indicated in Table 2. The resulting reaction
mixture was extracted with EtOAc (3 Â 10 mL). The organic phase was washed
with water and brine. Then, it was dried over anhydrous MgSO4, the solvent
was removed under reduced pressure, and the residue was purified by flash
chromatography on silica gel (EtOAc:hexanes 10/90). Spectral data of selected
products. Compound (3d): 1H NMR (200 MHz, CDCl3): d = 7.60–7.55 (m, 2H),
7.45–7.38 (m, 3H), 7.28–7.15 (m, 5H), 7.09–6.99 (m, 5H), 2.89 (s, 1H), 1.84 (s,
3H). 13C NMR (50 MHz, CDCl3): d = 144.5, 139.1, 135.5, 135.2, 135.1, 133.0,
129.3, 128.6, 128.2, 128.1, 127.9, 127.6, 127.2, 125.6, 78.3, 28.8. MS (EI): m/z
366 (M+, 27), 257 (13), 239 (10), 212 (100), 211 (55), 178 (45), 167 (35), 155
(36), 121 (25), 77 (15). Anal. Calcd for C22H19ClOS: C, 72.02; H, 5.22. Found: C,
71.63; H, 5.45. Compound (3e): 1H NMR (400 MHz, CDCl3): d = 7.56 (d, 2H,
J = 8.7), 7.40 (d, 2H, J = 8.8), 7.28 (s, 1H), 7.24–7.14 (m, 5H), 6.92 (d, 2H, J = 8.9),
6.55 (d, 2H, J = 8.9), 3.66 (s, 3H), 3.03 (s, 1H), 1.81 (s, 3H). 13C NMR (100 MHz,
CDCl3): d = 158.4, 144.8, 141.5, 135.6, 134.4, 132.9, 130.7, 129.4, 128.1, 127.9,
127.8, 127.2, 125.5, 114.4, 78.2, 55.2, 29.0. MS (EI): m/z 396 (M+, 16), 395 (63),
241 (100), 225 (55), 210 (36), 197 (53), 165 (32), 139 (58), 77 (25). Anal. Calcd
10. Uma, R.; Crévisy, C.; Grée, R. Chem. Rev. 2003, 103, 27.
11. (a) Barchi, J. J., Jr.; Moore, R. E.; Patterson, G. M. L. J. Am. Chem. Soc. 1984, 106,
8193; (b) Bollag, D. M.; McQueney, P. A.; Zhu, J.; Hensens, O.; Koupal, L.; Liesch,
J.; Goetz, M.; Lazarides, E.; Woods, C. M. CancerRes. 1995, 55, 2325; (c) Oka, M.;
Iimura, S.; Tenmyo, O.; Sawada, Y.; Sugawara, M.; Ohkusa, N.; Yamamoto, H.;
Kawano, K.; Hu, S.-L.; Fukagawa, Y.; Oki, T. J.Antibiot. 1993, 46, 367; (d) Burke, S.
D.; Hong, J.; Lennox, J. R.; Mongin, A. P. J. Org. Chem. 1998, 63, 6952; (e) Jamison,
F.; Chan, J. J. Am. Chem. Soc. 2003, 125, 11514.
12. (a) Takai, K.; Kataoka, Y.; Utimoto, K. J. Org. Chem. 1990, 55, 1707; (b) Magriotis,
P. A.; Brown, J. T.; Scott, M. E. Tetrahedron Lett. 1991, 32, 5050; (c) Ogawa, A.;
Tsuboi, Y.; Obayashi, R.; Yokoyama, K.; Ryu, I.; Sonoda, N. J. Org. Chem. 1994, 59,
1600; (d) Dabdoub, M. J.; Begnini, M. L.; Guerrero, P. G., Jr.; Baroni, A. C. M. J.
Org. Chem. 2000, 65, 61; (e) Langille, N. F.; Jamison, T. F. Org. Lett. 2006, 8, 3761;
(f) Kerrigan, M. H.; Jeon, S.; Chen, Y. K.; Salvi, L.; Carroll, P. J.; Walsh, P. J. J. Am.
Chem. Soc. 2009, 131, 8434.
13. (a) Doi, T.; Yanagisawa, A.; Miyazawa, M.; Yamamoto, K. Tetrahedron:
Asymmetry 1995, 6, 389; (b) Lee, T.; Kim, S. Tetrahedron: Asymmetry 2003, 14,
1951.
14. Murphy, J. A.; Patterson, C. W. J. Chem Soc., Perkin Trans 1 1993, 405.
15. (a) Stille, J. K. Angew. Chem. 1986, 25, 508; (b) Farina, V.; Krishnamurthy, V.;
Scott, W. Org.React. 1997, 50, 1.
16. (a) Whitham, G. H. In Organosulfur Chemistry; Davies, S. G., Ed.; Oxford
Chemistry Primers, Oxford University University Press: Oxford, 1995; (b)
Irgolic, K. I. In Houben-Weyl Methods of Organic Chemistry; Klaman, D., Ed.;
Georg Thieme: Stuttgart, 1990; 4th ed.; Vol. E12b, (c) Paulmier, C. Selenium
Reagents and Intermediates in OrganicSynthesis; Pergamon Press: Oxford, 1986;
(d) Petragnani, N.; Stefani, H. A. Tellurium in Organic Synthesis – Best Synthetic
Methods, 2nd ed.; Academic Press: London, 2007; (e) Cremlyn, R. J. An
Introduction to Organo-Sulfur Chemistry; Wiley & Sons: New York, 1996.
17. (a) Nogueira, C. W.; Zeni, G.; Rocha, J. B. T. Chem. Rev. 2004, 104, 6255; (b)
Zheng, Y. F.; Dodd, S. S.; Oehlschlager, A. C.; Hartman, P. G. Tetrahedron 1995,
51, 5255; (c) Ceruti, M.; Balliano, G.; Rocco, F.; Milla, P.; Arpico, S.; Cattel, L.;
Viola, F. Lipids 2001, 36, 629; (d) Zhao, G.; Zhou, Z. S. Bioorg. Med. Chem. Lett.
2001, 11, 2331; (e) Marcantoni, E.; Massaccesi, M.; Petrini, M. J. Org.Chem.
2000, 65, 4553; (f) Kabir, M. S.; Lorenz, M.; Van Linn, M. L.; Namjoshi, O. A.; Ara,
S.; Cook, J. M. J. Org.Chem. 2010, 75, 3626. and references therein..
18. (a) Zeni, G.; Ludtke, D. S.; Panatieri, R. B.; Braga, A. L. Chem. Rev. 2006, 106,
1032; (b) Silveira, C. C.; Perin, G.; Jacob, R. G.; Braga, A. L. Phosphorus, Sulfur,
Silicon Relat. Elem. 2001, 172, 309; (c) Perin, G.; Lenardão, E. J.; Jacob, R. G.;
Panatieri, R. B. Chem. Rev. 2009, 109, 1277.
for C23H21ClO2S: C, 69.60; H, 5.33. Found: C, 69.32; H, 5.33. Compound (3g): 1
H
NMR (200 MHz, CDCl3): d = 7.58–7.54 (m, 2H), 7.43 (s, 1H), 7.19–6.97 (m, 8H),
2.16 (s, 1H), 1.88–1.63 (m, 9H), 1.29–1.11 (m, 1H). 13C NMR (50 MHz, CDCl3):
d = 140.5, 136.5, 135.9, 135.3, 129.2, 128.6, 127.8, 127.7, 126.9, 125.1, 76.0,
36.3, 25.3, 21.9. MS (EI): m/z 310 (M+, 7), 292 (38), 183 (55), 167 (20), 141
(100), 125 (17), 115 (28), 91 (34), 77 (17), 55 (11). Anal. Calcd for C20H22OS: C,
77.38; H, 7.14. Found: C, 77.19; H, 7.01. Compound (3h): 1H NMR (200 MHz,
CDCl3): d = 7.60–7.56 (m, 2H), 7.43 (s, 1H), 7.24–6.98 (m, 8H), 2.49 (s, 1H), 1.52
(s, 6H). 13C NMR (50 MHz, CDCl3): d = 139.8, 136.2, 135.7, 134.9, 129.2, 128.6,
127.8, 127.8, 127.0, 125.2, 75.3, 29.4. MS (EI): m/z 270 (M+, 9), 252 (17), 211
(8), 143 (100), 128 (69), 115 (21), 77 (16). Anal. Calcd for C17H18OS: C, 75.51; H,
6.71 Found: C, 75.28; H, 6.71. Compound (3j):21c 1H NMR (400 MHz, CDCl3):
d = 7.43 (d, 2H, J = 8.4), 7.35–7.17(m, 8H), 6.43 (t, 1H, J = 6.8), 2.82 (s, 1H), 2.35–
2.22 (m, 1H), 2.21–2.04 (m, 1H), 1.75 (s, 3H), 1.43–1.21 (m, 4H),0.84 (t, 3H,
J = 7.2). 13C NMR (100 MHz, CDCl3): d = 146.4, 139.4, 139.1, 136.8, 128.7, 128.0,
127.1, 126.9, 125.5, 125.2, 78.0, 30.7, 30.1, 28.8, 22.3, 13.7. MS (EI): m/z 312
(M+, 33), 192 (86), 149 (83), 121 (57), 110 (100), 77 (34).
28. Sanz, R.; Martínez, A.; Lvarez-Gutiérrez, J. M.; Rodríguez, F. Eur. J. Org. Chem.
2006, 1383.
29. Inada, Y.; Nishibayashi, Y.; Hisai, M.; Uemura, S. J. Am. Chem. Soc. 2002, 124,
15172.
30. Georgy, M.; Boucard, V.; Campagne, J. M. J. Am. Chem. Soc. 2005, 127, 14180.
31. Zhan, Z. P.; Yu, J. L.; Liu, H. J.; Cui, Y. Y.; Yang, R. F.; Yang, W. Z.; Li, J. P. J.
Org.Chem. 2006, 71, 8298.
19. (a) Beletskaya, I. P.; Ananikov, V. P. Chem. Rev. 2011, 111, 1596; (b) Alonso, F.;
Beletskaya, I. P.; Yus, M. Chem. Rev. 2004, 104, 3079; (c) Gerard, J.; Hevesi, L.
Tetrahedron 2001, 57, 9109; (d) Kondo, T.; Mitsudo, T. Chem.Rev. 2000, 100,
3205.
Please cite this article in press as: Silveira, C. C.; et al. Tetrahedron Lett. (2013), http://dx.doi.org/10.1016/j.tetlet.2013.07.142