Palladium-catalyzed desulfitative C-H arylation of azoles with sodium sulfinates

Article abstract of DOI:10.1039/c1ob06387a

A palladium-catalyzed desulfitative C-H arylation of azoles with sodium sulfinates using Cu(OAc)₂·H₂O as oxidant has been discovered. The reaction proceeded well for a range of different substrates under oxidative conditions. A series of aryl-substituted azoles have been synthesized in moderate to good yields.

Full text of DOI:10.1039/c1ob06387a

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Palladium-catalyzed desulfitative C–H arylation of azoles with sodium
sulfinates†
Ru Chen, Saiwen Liu, Xinhua Liu, Luo Yang and Guo-Jun Deng*
Received 14th August 2011, Accepted 2nd September 2011
DOI: 10.1039/c1ob06387a
A palladium-catalyzed desulfitative C–H arylation of azoles
with sodium sulfinates using Cu(OAc) O as oxidant has
been discovered. The reaction proceeded well for a range of
different substrates under oxidative conditions. A series of
aryl-substituted azoles have been synthesized in moderate to
good yields.
Compared to the active and moisture-sensitive arenesulfonyl
chlorides, arenesulfinic acid sodium salts are comparably stable
and easy to handle. Thus, arenesulfinic acid sodium salts have
the potential to serve as ideal aryl sources for C–C bond forming
2
·H
2
17
reactions via SO release. In 1992, Sato and Okoshi reported an
2
efficient palladium-catalyzed desulfitative biaryl synthesis between
sulfinic acid sodium salts and aromatic bromides under harsh
18
conditions. Since then, however, little progress has been made
in this field. Very recently, we and others developed various
palladium-catalyzed desulfitative Heck-type coupling and aryl
ketone forming reactions between sodium sulfinates and nitriles
Aryl-substituted azoles are common building blocks for the syn-
thesis of pharmaceuticals, natural products, functional materials,
1
and many other biologically active molecules. The conventional
approaches for the preparation of these important compounds
mainly rely on either the cross-coupling of 2-aminophenol (or
19
(
or aldehydes) under relatively mild reaction conditions. The
2
desulfitative reactions are not very sensitive to moisture. The
extension of this methodology to the direct C–H arylation of
azoles would afford a straightforward and alternative synthetic
route to aryl-substituted azoles. In continuation of our interest
in using aromatic sulfinic acids (salts) as aryl sources under
mild reaction conditions, herein we describe the first palladium-
catalyzed desulfitative arylation of azoles with aromatic sodium
sulfinates via C–H activation. (Scheme 1).
thiophenol) in the presence of Lawesson’s reagent or the metal-
3
catalyzed intramolecular cyclization of thioformanilides. Over
the past decades, the activation of C–H bonds has received much
attention for the straightforward construction of C–C and C–
4,5
hetero bonds. This strategy is even more appealing for the
functionalization of heteroaromatic substrates due to problematic
6
homocoupling and poor stability under oxidative conditions.
Over the past several years, aryl-substituted azoles have been
successfully synthesized by direct C–H activation and subsequent
7
8
C–C bond formation with aryl halides, arylsilanes, aromatic
9
10
carboxylic acids, aryl boronic acids, and aryl triflates (or
11
mesylates and sulfamates). Recently, the groups led by Hu and
You, Ofial, Yamaguchi and Itami, and Zhang and Li successfully
developed various efficient palladium-catalyzed dehydrogenative
cross-couplings (CDC) of two heteroarenes which obviate the
need for any preactivation of the substrates.
Scheme 1 General desulfitative C–H arylation of azoles.
12
13
We began our study by examining the reaction of benzothiazole
(
1a) with p-toluenesulfinic acid sodium salt (2a) in N-methyl-2-
Arenesulfonyl chlorides are active compounds and are used as
starting materials for preparing compounds containing sulfonyl
pyrrolidone (NMP)/diglyme by using Pd(OAc)
2
as catalyst and
◦
14
oxygen as oxidant at 120 C. The desired product was obtained
groups. They are also used as aryl sources for C–C bond
forming reactions via desulfitative Heck type reactions under harsh
conditions. The first palladium-catalyzed desulfitative C–C bond-
forming reactions with arenesulfonyl chlorides were developed by
Kasahara et al. and Miura and co-workers under high reaction
1
in 42% yield as determined by GC and H NMR methods
(Table 1, entry 1). Other oxidants were tested under similar
reaction conditions (entries 2–6). The reaction yield could be
improved to 51% when TBHP (tert-butyl hydroperoxide) was
15
used. FeCl
transformation (entries 3 and 4). A good yield could be obtained
when CuCl O was used (entry 5). To our delight, the desired
3
and CuBr were not efficient oxidants for this kind of
2
temperature, and Dong and co-workers successfully extended
16
this strategy recently for direct arylation of 2-phenylpyridines.
2
·H
2
product 2-p-tolylbenzothiazole (3a) was obtained in 91% yield
when 2 equivalents of Cu(OAc) ·H O was used as the oxidant
Key Laboratory of Environmentally Friendly Chemistry and Application of
Ministry of Education, College of Chemistry, Xiangtan University, Xiangtan,
2
2
without adding any drying reagent (entry 6). Other palladium
4
11105, China. E-mail: gjdeng@xtu.edu.cn; Fax: (+86)-731-58292251;
Tel: (+86)-731-58298601
Electronic supplementary information (ESI) available: Experimental
salts were also investigated, using Cu(OAc)
2
·H
2
O as the oxidant.
Among them, PdCl and PdBr were inefficient catalysts and
2
2
†
details and characterization. See DOI: 10.1039/c1ob06387a
much lower yields were obtained (entries 7 and 8). Palladium
This journal is © The Royal Society of Chemistry 2011
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a
Table 1 Optimization of the reaction conditions
b
Entry
Catalyst
Oxidant
Solvent
Yield (%)
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
2
2
2
2
2
2
O
2
NMP/diglyme (1 : 3)
NMP/diglyme (1 : 3)
NMP/diglyme (1 : 3)
NMP/diglyme (1 : 3)
NMP/diglyme (1 : 3)
NMP/diglyme (1 : 3)
NMP/diglyme (1 : 3)
NMP/diglyme (1 : 3)
NMP/diglyme (1 : 3)
NMP/diglyme (1 : 3)
NMP/diglyme (1 : 3)
NMP/diglyme (1 : 3)
NMP/diglyme (3 : 1)
NMP/diglyme (1 : 1)
NMP/diglyme (1 : 2)
Dioxane/diglyme (1 : 3)
NMP
42
51
Trace
28
74
91
25
18
44
75
74
79
58
64
76
92
56
49
52
39
TBHP
FeCl
CuBr
CuCl
3
2
2
·H
2
O
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
Cu(OAc)
2
·H
·H
·H
·H
·H
·H
·H
·H
·H
·H
·H
·H
·H
·H
·H
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
O
O
O
O
O
O
O
O
O
O
O
O
O
O
O
PdCl
PdBr
Pd(CH
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
2
3
2 2
CN) Cl
0
1
2
3
4
5
6
7
8
9
0
Pd(acac)
Pd(OH)
Pd(NH
2
2
3
)
4
2
2
2
2
2
2
2
2
Cl
2
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Pd(OAc)
Diglyme
Dioxane
DMF
a
◦
b
Conditions: 1a (0.2 mmol), 2a (0.3 mmol), catalyst (2.5 mol%), oxidant (2 equiv.), 120 C, 24 h under air unless otherwise noted. GC yield based on
a.
1
a
Table 2 Desulfitative arylation of 2a with various heterocyclic compounds
b
Entry
1
Azole
Product
Yield (%)
1a
1b
3a
3b
83
2
76
40
c
3
1c
3c
c
4
1d
1e
1f
3d
3e
3f
56
45
81
88
78
81
c
5
6
7
8
9
1g
1h
1i
3g
3h
3i
1
0
1j
3j
42
a
◦
Conditions: 1 (0.2 mmol), 2a (0.3 mmol), Pd(OAc)
2
(2.5 mol%), Cu(OAc)
2
·H
2
O (2 equiv.), 1,4-dioxane (0.2 mL) and diglyme (0.6 mL), 120 C, 24 h
b
c
under air. Isolated yield. Solvent: N-methyl-2-pyrrolidone (0.2 mL) and diglyme (0.6 mL).
7
676 | Org. Biomol. Chem., 2011, 9, 7675–7679
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a
Table 3 Desulfitative arylation of 1a with various sodium sulfinates
b
Entry
1
Sodium sulfinate
Product
Yield (%)
2b
2c
3k
3l
71
2
75
c
3
2d
2e
2f
3m
3n
3o
3p
3q
70
58
68
50
35
c
4
5
6
2g
2h
c
7
c
8
2i
3r
86
a
◦
Conditions: 1a (0.2 mmol), 2 (0.3 mmol), Pd(OAc)
2
(2.5 mol%), Cu(OAc)
Isolated yield. Solvent: N-methyl-2-pyrrolidone (0.2 mL) and diglyme (0.6 mL).
2
·H
2
O (2 equiv.), 120 C, 1,4-dioxane (0.2 mL) and diglyme (0.6 mL), 24 h.
b
c
salts such as Pd(acac)
catalysts and gave the desired product in good yields (entries 10–
2). The solvent had a significant impact on the reaction yield.
2
, Pd(OH)
2
and Pd(NH
3
)
4
Cl
2
were efficient
with 2a afforded the desired product in 42% yield without further
optimization of the reaction conditions (about 50% caffeine left,
entry 10).
1
The reaction yield decreased significantly when the ratio of NMP
and diglyme changed (entries 13–15). A mixture of 1,4-dioxane
and diglyme was also a good solvent system and the desired
product was obtained in 92% yield (entry 16). Moderate yields
were obtained when the reaction was carried out in pure NMP,
diglyme, 1,4-dioxane and DMF (N,N-dimethylformamide), and
the desired product was obtained in 56%, 49%, 52% and 39%
yields, respectively (entries 17–20).
With the optimized reaction conditions in hand, we then
explored the scope and generality of this transformation. Var-
ious azoles bearing electron-withdrawing and donating sub-
stituents were investigated (Table 2). 6-Methoxybenzothiazole (1b)
smoothly coupled with 2a and gave the desired product in 76%
yield (Table 2, entry 2). A nitro group in the C6 position of
benzothiazole dramatically decreased the reaction yield (entry 3).
The reaction results of various arylsulfinic acid sodium salts
with benzothiazole 1a are presented in Table 3. A series of func-
tional groups including tert-butyl, methoxy, fluoro, chloro, bromo
and trifluoromethyl were tolerated under the optimal reaction
conditions, and the desired products were obtained in moderate
to good yields (entries 2–7). In general, electron-withdrawing
substituents on the aromatic sulfinic acids decreased the reaction
yields. More bulky substrates such as 2-naphthylsulfinic acid
sodium salt (2i) also reacted with 1a efficiently and gave the
product in 86% yield (entry 8).
A plausible mechanism to rationalize this transformation is
illustrated in Scheme 2. Take arylation of substrate 1a as an
example. First, the Pd(II) catalyst reacts with the benzothiazole
1a to form an Ar–Pd(II)–X intermediate A (X = OAc), which is
subsequently displaced by sulfinic acid 2 to form intermediate B.
This intermediate species undergoes desulfination to generate the
aryl-palladium complex C. A reductive elimination of C affords
the desired product 3 and the Pd(0) catalyst is reoxidized to Pd(II)
4
-Methylthiazole (1d) and 4,5-dimethylthiazole (1e) both reacted
with 2a and gave the desired products in moderate yields (entries
and 5). Benzoxazole and methyl-substituted benzoxazoles were
reacted with 2a and gave the desired products in high yields (entries
–8). A chloro moiety on benzoxazole was well tolerated under the
reaction conditions and afforded the desired product in 81% yield
entry 9). Caffeine is an important biologically active alkaloid
4
by Cu(OAc) , thus closing the catalytic cycle.
2
6
In summary, we have demonstrated a novel palladium-catalyzed
desulfitative direct arylation of azoles in the presence of an oxidant.
Various aromatic sulfinic acid sodium salts with or without sub-
stituents selectively coupled with azoles and afforded the adducts
(
with an imidazole motif. Notably, the coupling of caffeine (1j)
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and S. Murahashi, Chem. Rev., 1998, 98, 2599; (c) G. Dyker, Angew.
Chem., Int. Ed., 1999, 38, 1698; (d) C. Jia, T. Kitamura and Y. Fujiwara,
Acc. Chem. Res., 2001, 34, 633; (e) V. Ritleng, C. Sirlin and M. Pfeffer,
Chem. Rev., 2002, 102, 1731; (f) R. H. Crabtree, J. Organomet. Chem.,
2
6
004, 689, 4083; (g) L. Goj and T. Gunnoe, Curr. Org. Chem., 2005, 9,
71; (h) K. Godula and D. Sames, Science, 2006, 312, 67; (i) A. Dick
and M. S. Sanford, Tetrahedron, 2006, 62, 2439; (j) E. Beccalli, G.
Broggini, M. Martinelli and S. Sottocornola, Chem. Rev., 2007, 107,
5
1
2
318; (k) D. Alberico, M. Scott and M. Lautens, Chem. Rev., 2007,
07, 174; (l) L. Campeau, D. Stuart and K. Fagnou, Aldrichim. Acta,
007, 40, 35; (m) J. Lewis, R. Bergman and J. Ellman, Acc. Chem.
Res., 2008, 41, 1013; (n) B. Li, S. Yang and Z. Shi, Synlett, 2008,
49; (o) M. Diaz-Requejo and P. P e´ rez, Chem. Rev., 2008, 108, 3379;
p) M. Zhang, Adv. Synth. Catal., 2009, 351, 2243; (q) X. Chen, K.
Engle, D. Wang and J. Yu, Angew. Chem., Int. Ed., 2009, 48, 5094;
r) R. Giri, B. Shi, K. Engle, N. Maugel and J. Yu, Chem. Soc. Rev.,
9
(
(
2
1
009, 38, 3242; (s) T. Lyons and M. Sanford, Chem. Rev., 2010, 110,
147; (t) C. Cop e´ ret, Chem. Rev., 2010, 110, 656; (u) I. Mkhalid, J.
Scheme 2 Proposed mechanism.
Barnard, T. Marder, J. Murphy and J. Hartwig, Chem. Rev., 2010, 110,
8
90.
in moderate to good yields. Unlike decarboxylative coupling
reactions, no electron-withdrawing or -donating group ortho to
the sulfinic acid group was necessary to ensure the desulfitative
6 (a) K. Masui, H. Ikegami and A. Mori, J. Am. Chem. Soc., 2004, 126,
5074; (b) Z. Liang, J. Zhao and Y. Zhang, J. Org. Chem., 2010, 75, 170;
(
c) T. Kinzel, Y. Zhang and S. Buchwald, J. Am. Chem. Soc., 2010, 132,
4073 and references therein.
1
20
coupling. Functional groups such as methoxy, bromo, fluoro,
and chloro on the aromatic sulfinic acid sodium salts were all well
tolerated under these reaction conditions. This method affords an
alternative route for the synthesis of heteroaromatic biaryls. The
scope, mechanism, and synthetic applications of this reaction are
under investigation.
7
(a) Y. Kondo, T. Komine and T. Sakamoto, Org. Lett., 2000, 2, 3111;
(b) W. Gallagher and R. Maleczka, J. Org. Chem., 2003, 68, 6775;
(
c) A. Yokooji, T. Okazawa, T. Satoh, M. Miura and M. Nomura,
Tetrahedron, 2003, 59, 5685; (d) B. Sezen and D. Sames, Org. Lett.,
003, 5, 3607; (e) J. Lewis, S. Wiedemann, R. Bergman and J. Ellman,
2
Org. Lett., 2004, 6, 35; (f) H. Chiong and O. Daugulis, Org. Lett., 2007,
9, 1449; (g) G. Turner, J. Morris and M. Greaney, Angew. Chem., Int.
Ed., 2007, 46, 7996; (h) H. Do and O. Daugulis, J. Am. Chem. Soc., 2007,
1
29, 12404; (i) R. S a´ nchez and F. Zhuravlev, J. Am. Chem. Soc., 2007,
Acknowledgements
129, 5824; (j) F. Derridj, S. Djebbar, O. Benali-Baitich and H. Daucet, J.
Organomet. Chem., 2008, 693, 135; (k) N. Nandurkar, M. Bhanushali,
M. Bhor and B. Bhanage, Tetrahedron Lett., 2008, 49, 1045; (l) J. Lewis,
A. Berman, R. Bergman and J. Ellman, J. Am. Chem. Soc., 2008, 130,
This work was supported by the National Natural Science Founda-
tion of China (21172185, 20902076), the HunanProvincialNatural
Science Foundation of China (11JJ1003), the One Hundred Talent
Project of Hunan Province and the Academic Leader Program
2
2
493; (m) J. Canivet, J. Yamaguchi, I. Ban and K. Itami, Org. Lett.,
009, 11, 1733; (n) O. Dogan, N. Guerbuez, I. Oezdemir, B. Cetinkaya,
O. Sahin and O. Bueguekguengoer, Dalton Trans., 2009, 7087; (o) T.
Miyaoku and A. Mori, Heterocycles, 2009, 77, 151; (p) D. Zhao, W.
Wang, F. Yang, J. Lan, L. Yang, G. Gao and J. You, Angew. Chem.,
Int. Ed., 2009, 48, 3296; (q) J. Huang, J. Chan, Y. Chen, C. Borths, K.
Kyle, R. Larsen and M. Margaret, J. Am. Chem. Soc., 2010, 132, 3674;
(
09QDZ12) of Xiangtan University.
Notes and references
(
r) F. Shibahara, E. Yamaguchi and T. Murai, Chem. Commun., 2010,
1
(a) L. Zirngibl, Antifungal Azoles: A Comprehensive Survey of Their
Structures and Properties, Wiley-VCH, Weinheim, 1998; (b) Compre-
hensive Heterocyclic Chemistry III, Vol.11, ed. A. R. Katritzky, C. W.
Rees and E. F. Scriven, Pergamon, Oxford, 1999; (c) A. Katritzky and
A. Pozharskii, Handbook of Heterocyclic Chemistry, 1st edn, Pergamon,
Oxford, 2003. For selected reviews, see: (d) A. Kraft, A. Grimsdale and
A. Holmes, Angew. Chem., Int. Ed., 1998, 37, 402; (e) K. C. Nicolaou, P.
G. Bulger and D. Sarlah, Angew. Chem., Int. Ed., 2005, 44, 4442; (f) J. S.
Carey, D. Laffan, C. Thomson and M. T. Williams, Org. Biomol. Chem.,
46, 2471; (s) D. Saha, L. Adak and B. C. Ranu, Tetrahedron Lett., 2010,
51, 5624; (t) F. Shibahara, E. Yamaguchi and T. Murai, J. Org. Chem.,
2011, 76, 2680; (u) T. Yamamoto, K. Muto, M. Komiyama, J. Canivet,
J. Yamaguchi and K. Itami, Chem.–Eur. J., 2011, 17, 10113.
8 H. Hachiya, K. Hirano, T. Satoh and M. Miura, Angew. Chem., Int.
Ed., 2010, 49, 2202.
9 F. Z. Zhang and M. F. Greaney, Angew. Chem., Int. Ed., 2010, 49, 2768.
10 (a) S. K. Guchhait, Kashyap and S. Saraf, Synthesis, 2010, 1166; (b) B.
Liu, X. Qin, K. Li, X. Li, Q. Guo, J. Lan and J. You, Chem.–Eur. J.,
2010, 16, 11836; (c) S. Ranjit and X. Liu, Chem.–Eur. J., 2011, 17, 1105;
(d) S. Kirchberg, S. Tani, K. Ueda, J. Yamaguchi, A. Studer and K.
Itami, Angew. Chem., Int. Ed., 2011, 50, 2387.
11 (a) J. Roger and H. Doucet, Org. Biomol. Chem., 2008, 6, 169; (b) C. So,
C. Lau and F. Kwong, Chem.–Eur. J., 2011, 17, 761; (c) L. Ackermann,
S. Barfusser and J. Pospech, Org. Lett., 2010, 12, 724.
2
006, 4, 2337; (g) D. S. Surry and S. L. Buchwald, Angew. Chem., Int.
Ed., 2008, 47, 6338.
2
3
For a review, see: (a) T. Ozturk, E. Ertas and O. Mert, Chem. Rev., 2007,
1
07, 5210. For selected examples, see: (b) C. Benedi, F. Bravo, P. Uriz,
E. Fernandez, C. Claver and S. Castillon, Tetrahedron Lett., 2003, 44,
073; (c) D. Bernardi, L. A. Ba and G. Kirsch, Synlett, 2007, 2121.
(a) B. Zou, Q. Yuan and D. Ma, Angew. Chem., Int. Ed., 2007, 46, 2598;
b) D. S. Bose, M. Idrees and B. Srikanth, Synthesis, 2007, 819; (c) Y.
6
12 For a review on CDC reactions: C. J. Li, Acc. Chem. Res., 2009, 42,
335.
(
Chen, X. Xie and D. Ma, J. Org. Chem., 2007, 72, 9329; (d) F. Liu and
D. Ma, J. Org. Chem., 2007, 72, 4884; (e) T. Itoh and T. Mase, Org.
Lett., 2007, 9, 3687; (f) D. Ma, S. Xie, P. Xue, X. Zhang, J. Dong and
Y. Jiang, Angew. Chem., Int. Ed., 2009, 48, 4222; (g) J. Peng, C. Zong,
M. Ye, T. Chen, D. Gao, Y. Wang and X. Chen, Org. Biomol. Chem.,
13 For reviews and highlights, see: (a) X. Bugaut and F. Glorius, Angew.
Chem., Int. Ed., 2011, 50, 7479; (b) D. Zhao, J. You and C. Hu, Chem.–
Eur. J., 2011, 17, 5466. For selected examples, see: (c) P. Xi, F. Yang, S.
Qin, D. Zhao, J. Lan, G. Gao, C. Hu and J. You, J. Am. Chem. Soc.,
2010, 132, 1822; (d) W. Han, P. Mayer and A. R. Ofial, Angew. Chem.,
Int. Ed., 2011, 50, 2178; (e) C. Malakar, D. Schmidt, J. Conrad and U.
Beifuss, Org. Lett., 2011, 13, 1378; (f) Z. Wang, K. Li, D. Zhao, J. Lan
and J. You, Angew. Chem., Int. Ed., 2011, 50, 5365; (g) A. Yamaguchi,
D. Mandal, J. Yamaguchi and K. Itami, Chem. Lett., 2011, 40, 555;
(h) X. Gong, G. Song, H. Zhang and X. Li, Org. Lett., 2011, 13,
1766.
2
011, 9, 1225.
4
5
(a) G. Dyker, Handbook of C–H Transformations: Applications in
Organic Synthesis, Wiley-VCH, Weinheim, 2005; (b) C–H Activation,
ed. J. Yu and Z. Shi, Springer, Berlin, Germany, 2010; (c) Activation and
Functionalization of C–H Bond, ed. K. I. Goldberg and A. S. Goldman,
ACS Symposium Series 885, 2004.
For representative reviews on C–H functionalization, see: (a) A. Shilov
and G. Shul’pin, Chem. Rev., 1997, 97, 2879; (b) T. Naota, H. Takaya
14 (a) P. Page, Organosulfur Chemistry: Stereochemical Aspects, Academic
Press, Inc., San Diego, 1998; (b) S. Dubbaka and P. Vogel, Angew.
7
678 | Org. Biomol. Chem., 2011, 9, 7675–7679
This journal is © The Royal Society of Chemistry 2011

View Article Online
Chem., Int. Ed., 2005, 44, 7674; (c) N. Simpkins, Sulfones in Organic
Synthesis, Pergamon Press, Oxford, 1993.
16 X. Zhao, E. Dimitrijevi c´ and V. Dong, J. Am. Chem. Soc., 2009, 131,
3466.
17 For early investigations on desulfitative reaction using sulfinic acid
(salt), see: (a) K. Garves, J. Org. Chem., 1970, 35, 3273; (b) R. Selke
and W. Thiele, J. Prakt. Chem., 1971, 313, 875; (c) E. Wenkert, T.
Ferreira and E. Michelotti, J. Chem. Soc., Chem. Commun., 1979,
637.
18 K. Sato and T. Okoshi, Patent US5159082, 1992.
19 (a) X. Zhou, J. Luo, J. Liu, S. Peng and G. Deng, Org. Lett., 2011, 13,
1432; (b) J. Liu, X. Zhou, H. Rao, F. Xiao, C. Li and G. Deng, Chem.–
Eur. J., 2011, 17, 7996; (c) H. Yao, L. Yang, Q. Shuai and C. Li, Adv.
Synth. Catal., 2011, 353, 1701; (d) G. Wang and T. Miao, Chem.–Eur.
J., 2011, 17, 5787; (e) T. Miao and G. Wang, Chem. Commun., 2011,
47, 9501.
20 For reviews on decarboxylative couplings, see: (a) L. Goossen,
N. Rodr ´ı guez and K. Goossen, Angew. Chem., Int. Ed., 2008, 47,
3100; (b) N. Rodr ´ı guez and L. J. Goossen, Chem. Soc. Rev., 2011,
DOI: 10.1039/c1cs15093f.
1
5 For desulfitative C–C bond formation using sulfonyl chlorides as
starting materials, see: (a) A. Kasahara, T. Izumi, N. Kudou, H. Azami
and S. Yamamato, Chem. Ind., 1988, 51; (b) A. Kasahara, T. Izumi,
K. Miyamoto and T. Sakai, Chem. Ind., 1989, 192; (c) M. Miura, H.
Hashimoto, K. Itoh and M. Nomura, Tetrahedron Lett., 1989, 30, 975;
(
d) M. Miura, H. Hashimoto, K. Itoh and M. Nomura, J. Chem. Soc.,
Perkin Trans. 1, 1990, 2207; (e) S. Dubbaka and P. Vogel, J. Am. Chem.
Soc., 2003, 125, 15292; (f) S. Dubbaka and P. Vogel, Org. Lett., 2004,
6
, 95; (g) S. Dubbaka, P. Steunenberg and P. Vogel, Synlett, 2004, 1235;
(
h) S. Dubbaka and P. Vogel, Adv. Synth. Catal., 2004, 346, 1793; (i) S.
Dubbaka and P. Vogel, Chem.–Eur. J., 2005, 11, 2633; (j) S. Dubbaka,
D. Zhao, Z. Fei, C. Volla, P. Dyson and P. Vogel, Synlett, 2006, 3155;
(
k) C. Rao and P. Vogel, Angew. Chem., Int. Ed., 2008, 47, 1305; (l) C.
Volla, S. Dubbaka and P. Vogel, Tetrahedron, 2009, 65, 504; (m) C.
Volla, D. Markovic, S. Dubbaka and P. Vogel, Eur. J. Org. Chem., 2009,
6
281.
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