Manganese(III) Acetate Mediated C–H Sulfonylation of 1,4-Dimethoxybenzenes with Sodium and Lithium Sulfinates

Article abstract of DOI:10.1002/ejoc.201700713

A simple and mild Mn(OAc)₃-promoted oxidative coupling of 1,4-dimethoxybenzenes with sodium and lithium sulfinates was developed. The reaction proceeded readily at room temperature in air, and various sulfones were synthesized in moderate to high yields. In addition, a straightforward approach for the conversion of organolithium reagents and sulfur dioxide into sulfonylated 1,4-dimethoxybenzenes was explored.

Full text of DOI:10.1002/ejoc.201700713

A Journal of
Accepted Article
Title: Mn(OAc)3-Mediated C-H-Sulfonylation of 1,4
Dimethoxybenzenes with Sodium and Lithium Sulfinates
Authors: Shuai Liang, Yueling Ren, and Georg Manolikakes
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To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201700713
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10.1002/ejoc.201700713
European Journal of Organic Chemistry
COMMUNICATION
Mn(OAc)3-Mediated C-H-Sulfonylation of 1,4-Dimethoxybenzenes
with Sodium and Lithium Sulfinates
Shuai Liang, Yueling Ren and Georg Manolikakes*
Dedicated to Prof. Herbert Mayr on the occasion of his 70th birthday
Abstract: A simple and mild Mn(OAc)3-promoted oxidative coupling
of 1,4-dimethoxybenzenes with sodium and lithium sulfinates has
been developed. The reaction proceeds readily at room temperature
in air and various sulfones were synthesized in moderate to high
yields. In addition, a straightforward approach for the conversion of
organolithium reagents and sulfur dioxide into sulfonylated 1,4-
dimethoxybenzenes is reported.
Common approaches for the synthesis of these compounds are
the oxidation of the corresponding sulfides,[13] the addition of
sulfinic acids or sulfinates to benzoquinones[14] or the reactions
of hydroquinone derivatives with sulfonyl chlorides.[15] Recently,
the groups of Wang and Wei reported different procedures for
the direct C-H-functionalization of benzoquinones with sulfonyl
chlorides or hydrazides.[16] Herein, we wish to report
complementary approach, Mn(OAc)3-promoted cross-
a
a
dehydrogenative coupling of 1,4-dimethoxybenzene with sodium
and lithium sulfinates.
Introduction
Sulfones are important synthetic intermediates in organic
chemistry and have found widespread application in the
pharmaceutical and agrochemical industry and in material
science.[1] The sulfone moiety is of particular importance for
medicinal chemistry. Various drugs, such as the non-steroidal
antiandorgen casodex[2] or the antibiotic dapsone,[3] contain a
sulfone group.
Traditional methods for the synthesis of sulfones are the
oxidation of sulfides, Friedel-crafts-type reactions with sulfonyl
chlorides and the addition of sulfonyl-based radicals to double or
triple bonds.[1,4] More recently, methods based on sulfinic acid
salts have become an attractive alternative.[5,6] Various three-
component reactions based on the in situ formation of sulfinates
using sulfur dioxide or suitable surrogates[7] have been reported
in the last five years.[8] Concurrently, the sustainable synthesis of
sulfones via the selective functionalization of C-H-bonds has
gained more attention.[9,10]
Results and Discussion
In the course of our efforts towards highly modular and
sustainable procedures for the synthesis of sulfones[8d,h] and
sulfonamides,[17] we could identify the combination of a copper
catalyst with Mn(OAc)3 in 1,1,1,3,3,3-hexafluoroisopropanol
(HFIP) as highly efficient reaction system for the cross-oxidative
C-H-sulfonylation of 8-aminoquinolines or anilines.[18] We
envisioned, that this system should be able to promote similar
cross-dehydrogenative coupling reaction of sulfinic acid salts
with other oxidation-prone substrates.
Indeed, the reaction of 1,4-dimethoxybenzene (1a) with sulfinate
2a in the 20 mol% Cu(OAc)2 and stoichiometric amounts of
.
Mn(OAc)3 H2O in HFIP furnished the desired sulfone 3a in 69%
yield (Table 1, entry 1). Interestingly, the reaction proceeded
more efficiently in the absence of a copper catalyst, delivering
the product 3a in 78% yield (entry 2). HFIP is crucial for an
efficient reaction.[19] No product formation was observed in any
other solvent, such as trifluoroethanol (TFE), acetic acid (AcOH)
or CH2Cl2 (entries 3-6). In a similar manner, the choice of
Sulfonylated benzoquinone and hydroquinone derivatives
display a variety of interesting biological properties, e.g. c-jun-N-
terminal kinase-1 (JNK-1) inhibition[11] or marked cyctotoxic
activity (Figure 1).[12]
.
Mn(OAc)3 2H2O is essential for a successful transformation.[20]
Various
other
oxidants,
e.g.
2,3-dichloro-5,6-
OMe
OMe
NH2
N
OMe
O O
O
O
dicyanobenzoquinone (DDQ), Cu(OAc)2, FeCl3, tert-butyl
hydroperoxide (TBHP) or K2S2O8 did not furnish the desired
product at all (entries 7-11). Only in the case of the PhI(OAc)2, a
hypervalent iodine reagent which has been utilized in the
oxidative functionalization of phenol ethers,[21] minor amounts of
sulfone 3a were formed (entry 12). In general, the use of other
oxidants led to a fast decomposition of the sulfinate 2a. The
reason for the specific reactivity of Mn(OAc)3 remains unclear
and is currently under investigation in our laboratory.
S
CN
S
OMe
Me
O
Me
N
OEt
H
OMe O
JNK-1 inhibitor
Potential chemotherapeutic agent
Figure 1. Selected biologically active 1,4-dimethoxybenzenes containing a
sulfone moiety.
With the optimized reaction conditions at hand, we explored the
reaction of 1,4-dimethoxybenzene (1a) with different sodium
sulfinates 2 (Scheme 1). Aryl sulfinates bearing electron-
withdrawing or electron-donating groups reacted smoothly,
providing the diarylsulfones 3a-3i in 52-90% yield. Halogen-
substituted sulfinic acid salts were well tolerated, and furnished
the sulfones 3d-3f, bearing potential handles for further
manipulations, in 77-90% yield. Contrary to our previous copper-
catalyzed reactions,[18] the heterocyclic 2-pyridine sulfinate
[a]
S. Liang, Y. Ren, G. Manolikakes
Institute of Organic Chemistry and Chemical Biology
Goethe-University Frankfurt
Max-von-Laue-Str. 7, D-60438 Frankfurt am Main, Germany
E-mail: g.manolikakes@chemie.uni-frankfurt.de
Homepage: https://www.uni-frankfurt.de/53469467/Manolikakes
Supporting information for this article is given via a link at the end of
the document.((Please delete this text if not appropriate))
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10.1002/ejoc.201700713
European Journal of Organic Chemistry
COMMUNICATION
MeO
MeO
MeO
MeO
O
S
O
proved to be a suitable substrate, affording the heteroarylsulfone
3j in 57% yield. The reactions of sodium naphthylsulfinate (2k)
and sodium methyl sulfinate (2j) furnished the corresponding
naphthyl sulfone 3k in 72% yield and the methyl sulfone 3j in
55% yield, respectively.
H
Mn(OAc)3.2H2O
HFIP, 25 °C, 2h
R
+
R
SO2Na
1a
2
3
MeO
MeO
MeO
MeO
O
O
S
O
O
S
O
O
S
Table 1. Optimization of the reaction parameters.[a]
Alk
Hal
OMe
MeO
MeO
O
S
O
MeO
MeO
NaO2S
H
oxidant
+
3a: 78% (Alk = Me)
3b: 52% (Alk = tBu)
3c: 67%
3d: 88% (Hal = F)
3e: 90% (Hal = Cl)
3f: 77% (Hal = Br)
solvent
25 °C
Me
Me
OMe
1a
2a
Oxidant
3a
MeO
MeO
MeO
O
S
O
O
S
O
O O
S
Yield [%|[b]
entry
Solvent
CF3
OMe
NO2
MeO
MeO
MeO
MeO
[c]
1
2
Cu(OAc)2 and Mn(OAc)3
Mn(OAc)3
Mn(OAc)3
Mn(OAc)3
Mn(OAc)3
Mn(OAc)3
DDQ
HFIP
HFIP
TFE
69
78
-
3g: 78%
MeO
3h: 83%
3i: 56%
MeO
O O
O
S
O
O
O
S
S
Me
3
N
4
CH3CN
AcOH
CH2Cl2
HFIP
HFIP
HFIP
HFIP
HFIP
HFIP
-
MeO
MeO
MeO
3l: 55%
3j: 57%
3k: 72%
5
-
Scheme 1. Substrate scope of sodium sulfinates. Yields of isolated products
6
-
are given.
7
-
8
Cu(OAc)
-
Next, we investigated reactions with the two unsymmetrical 1,4-
dihydroquinone derivatives 1b and 1c (Scheme 2). Unfortunately,
no regioselectivity was observed. The reaction of 1,4-dimethoxy-
2-methylbenzene (1b) with sodium para-chlorophenylsulfinate
(2e) led to the formation of the two regioisomeric sulfones 3m
and 3n in 37% and 51% yield. In the case of dihydroquinone 1c
bearing two different protecting groups the two regioisomers 3o
and 3p were obtained in 37% and 58% yield.
So far, the Mn(OAc)3-mediated oxidative C-H-sulfonylation is
limited to 1,4-dimethoxybenzene derivatives. Reactions with
other electron-rich arenes such as anisol (1d), 4-methylanisole
(1e), 1,2-dimethoxybenzene (1f), 1,3-dimethoxybenzene (1g),
1,3,5-trimethoxybenzene (1h) or para-Methoxyphenol (1i) did
not afford the desired product (Figure 2).[22]
9
FeCl3
-
10
11
12
TBHP
-
K2S2O8
-
PhI(OAc)2
11
[a] Reactions conditions: 1a (0.2 mmol), 2a (0.4 mmol), oxidant (0.6 mmol),
HFIP (2 mL), 25 °C, 2 h; [b] Isolated yield of analytical pure product; [c] with
0.04 mmol of Cu(OAc)2 and 0.6 mmol Mn(OAc)3 H2O.
.
MeO
MeO
MeO
MeO
MeO
O
S
O
O O
S
2e
Mn(OAc)3
Me
Me
+
OMe
OMe
OMe
OMe
OMe
OMe
HFIP
25 °C, 2h
Cl
Me
Cl
OMe
MeO
OMe
MeO
OMe
1b
3m: 37%
3n: 51%
Me
OH
1d
1e
1f
1g
1h
1i
TIPSO
MeO
TIPSO
MeO
O
S
O
O O
S
2e
Mn(OAc)3
Figure 2. Substrates not suitable for the Mn(OAc)3-mediated oxidative
sulfonylation.
+
HFIP
25 °C, 2h
Cl
Cl
MeO
TIPSO
1c
3o: 37%
3p: 58%
For the purpose of increasing the synthetic utility of our method,
we examined the coupling of lithium sulfinates, easily accesible
from the reaction of the corresponding organolithium compounds
with sulfur dioxide.[1,7] Thus, lithium benzene- and n-
butanesulfinates 4a and 4b were prepared from sulfur dioxide
and phenyllithium 5a or n-butyllithium 5b in quantitative yields
Scheme 2. Sulfonylation of 1,4-dihydroquinone derivatives 1b and 1c.
Yields of isolated prodcuts are given. TIPS = Triisopropylsilyl.
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10.1002/ejoc.201700713
European Journal of Organic Chemistry
COMMUNICATION
(Scheme 3a). To our delight, the crude sulfinates undergo an
efficient coupling with 1,4-dimethoxybenzene (1a) in the
presence of Mn(OAc)3 affording the desired sulfones 3c and 3q
in 72% and 78% yield. Reaction of para-toluene lithium sulfinate
(5c), prepared in a two-step sequence from 4-iodotoluene using
a lithium-halide exchange and subsequent trapping with sulfur
dioxide, furnished sulfone 3a in 92% yield (Scheme 3b). Lithium
Experimental Section
Typical procedure:
An oven dried 10 mL tube was charged with a magnetic stirring bar, 1,4-
dimethoxybenzene derivative 1 (1.0 equiv, 0.2 mmol), sodium sulfinate 2
(2.0 equiv, 0.4 mmol), Mn(OAc)3·2H2O (160.8 mg, 3.0 equiv, 0.6 mmol)
and HFIP (0.1 M referring to 1,4-dimethoxybenzene derivative, 2 mL).
The tube was closed with a rubber septum and the resulting reaction
mixture was stirred at room temperature for 2h. After completion of the
reaction, the mixture was diluted with ethyl acetate and filtered through a
short plug of celite and silica gel. The filter pad was rinsed with additional
ethyl acetate and the combined filtrates were concentrated under
reduced pressure. Purification of the crude residue by flash column
chromatography afforded the analytically pure product.
sulfinate
5d
was
synthesized
starting
from
1,3-
dimethoxybenzene via deprotonation, followed by reaction of the
formed organolithium compound with sulfur dioxide (Scheme 3c).
The Mn(OAc)3-mediated coupling of sulfinate 5d with 1,4-
dimethoxybenzene yielded diarylsulfone 3r in 66% yield. These
results demonstrate, that interesting sulfone scaffolds are
directly accessible from simple starting materials and sulfur
dioxide by merging classical organolithium chemistry with the
herein reported cross-dehydrogenative coupling.
Acknowledgements
Financial support by the Fonds der der Chemischen Industrie
(Liebig Fellowship to G.M.), the Boehringer Ingelheim
Foundation (Exploration Grant to G.M.) and the Chinese
Scholarship Council (PhD fellowship to S.L) is gratefully
acknowledged. We would like to thank Prof. Michael Göbel
(Goethe-University Frankfurt) for his support and Albemarle
(Frankfurt) for the generous donation of chemicals.
MeO
O
S
O
1a
a)
Mn(OAc)3 (3.0 equiv.)
SO2
R
R
SO2Li
R
Li
- 40 to 25 °C
HFIP, 25 °C, 2h
MeO
4a (R = Ph)
4b (R = n-Bu)
5a (R = Ph)
5b (R = n-Bu)
3c: 72% (R = Ph)
3q: 78% (R = n-Bu)
b)
I
SO2Li
MeO
MeO
O
S
O
1a
1) n-BuLi
0 °C
Mn(OAc)3 (3.0 equiv.)
Keywords: sulfone • C-H-functionalization • manganese • cross-
2) SO2
- 40 °C
HFIP, 25 °C, 2 h
dehydrogenative coupling • sulfinic acid
Me
Me
Me
6
5c
3a: 92%
[1]
a) S. Patai, C. Z. Rappoport, J. M. Stirling, The Chemistry of Sulfones
and Sulfoxides, Wiley, New York, 1988; b) N. S. Simpkins, Sulphones
in Organic Synthesis, Pergamon Press, Oxford, 1993; c) M. Feng, B.
Tang, S. H. Liang, X. Jiang, Curr. Top. Med. Chem. 2016, 16, 1200-
1216; d) H. Liu, X. Jiang, Chem. Asian J. 2013, 8, 2546-2563.
T. Gilligan, W. Oh, Prostate 2001, 3, 42–43.
1a
Mn(OAc)3
(3.0 equiv.)
MeO
OMe
O O
c)
OMe
OMe
1) n-BuLi
0 °C
S
SO2Li
2) SO2
- 40 °C
HFIP, 25 °C, 2h
OMe
OMe
MeO
[2]
[3]
MeO
C. Lopez, R. A. Pearlstein, A. J. Hopfinger, J. K. Seydel, J. Med. Chem.
1987, 30, 900–906.
7
5d
3r: 66%
[4]
[5]
N.-W. Liu, S. Liang, G. Manolikakes, Synthesis 2016, 1939.
J. Aziz, S. Messaoudi, M. Alami, A. Hamze, Org. Biomol. Chem. 2014,
12, 9743.
Scheme 3. Synthesis and oxidative coupling of lithium sulfinates. Yields of
isolated products are given.
[6]
For selected examples, see: a) G. Zhang, L. Zhang, H. Yi, Y. Luo, X. Qi,
C.-H. Tong, L.-Z. Wu A. Lei, Chem. Commun. 2016, 52, 10407; b) Q.
Lu, J. Zhang, F. Wei, Y. Qi, H. Wang, Z. Liu, A. Lei, Angew. Chem. Int.
Ed. 2013, 52, 7156; c) N. Umierski, G. Manolikakes, Org. Lett. 2013,
15, 188; d) A. Kar, I. A. Sayyed, W. F. Lo, H. M. Kaiser, M. Beller, M. K.
Tse, Org. Lett. 2007, 9, 3405; e) W. Zhu, D. Ma, J. Org. Chem. 2005,
70, 2696; f) S. Cacchi, G. Fabrizi, A. Goggiamani, L. M. Parisi, R.
Bernini, J. Org. Chem. 2004, 69, 5608 and references therein.
a) E. J. Emmett, M. C. Willis, Asian J. Org. Chem. 2015, 4, 602; b) G.
Liu, C. Fan, J. Wu, Org. Biomol. Chem. 2015, 13, 1592; c) A. S.
Deeming, E. J. Emmett, C. S. Richards-Taylor, M. C. Willis, Synthesis
2014, 2701.
Conclusions
In summary, we have developed a facile Mn(OAc)3-promoted
cross-dehydrogenative coupling of sodium and lithium sulfinates
with 1,4-dimethoybenzenes. The reaction is simple to perform
and proceeds readily at room temperature. Various functional
groups are tolerated and the products are obtained in good to
excellent yields. This novel method represents the first example
of a purely manganese-promoted oxidative coupling of sulfinic
acid salts and could offer a new, promising approach for the C-
H-functionalization of arenes or heteroarenes. In addition, the
[7]
[8]
For selected examples, see: a) D. Zhang, M. Chen, L. Yao, J. Wu, Org.
Chem. Front. 2016, 3, 985; b) A. S. Deeming, C. J. Russell, M. C.
Willis, Angew. Chem. Int. Ed. 2016, 55, 747; c) A. Shavnya, K. D. Hesp,
V. Mascitti, A. C. Smith, Angew. Chem. Int. Ed. 2015, 54, 13571; d) N.
Margraf, G. Manolikakes, J. Org. Chem. 2015, 80, 2582; e) B. N.
Rocke, K. B. Bahnck, M. Herr, S. Lavergne, V. Mascitti, C. Perreault, J.
Polivkova, A. Shavnya, Org. Lett. 2014, 16, 154; f) A. S. Deeming, C. J.
Russell, A. J. Hennessy, M. C. Willis, Org. Lett. 2014, 16, 150; g) E. J.
Emmett, B. R. Hayter, M. C. Willis, Angew. Chem. Int. Ed. 2013, 52,
12679; h) N. Umierski, G. Manolikakes, Org. Lett. 2013, 15, 4972 and
references therein.
combination with organolithium chemistry allows
a rapid
synthesis of complex sulfones from two simple building blocks
and sulfur dioxide. The unique role of Mn(OAc)3 in this reaction
and further applications of Mn(OAc)3 in oxidative coupling
reactions are currently under investigation in our laboratory.
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10.1002/ejoc.201700713
European Journal of Organic Chemistry
COMMUNICATION
[9]
a) C. Shen, P. Zhang, Q. Sun, S. Bai, T. S. A. Hor, X. Liu, Chem. Soc.
Rev. 2015, 44, 291; b) S. Shaaban, S. Liang, N.-W. Liu, G.
Manolikakes, Org. Biomol. Chem. 2017, 15, 1947.
Tetrahedron Lett. 2009, 50, 1407; c) M. Hosseini-Sarvari, Lett. Org.
Chem. 2008, 5, 425.
[16] a) X. Yu, Q. Wu, H. Wan, Z. Xu, X. Xu, D. Wang, RSC Adv. 2016, 6,
62298; b) L. Wang, Y.-B. Xie, Q.-L. Yang, M.-G. Liu, K.-B. Zheng, Y.-L.
Hu, N.-Y. Huang, J. Iran. Chem. Soc. 2016, 13, 1797; c) D. Wang, X.
Yu, B. Ge, H. Miao, Y. Ding, Chin. J. Org. Chem. 2015, 35, 676; d) B.
Ge, D. Wang, W. Dong, P. Ma, Y. Li, Y. Ding, Tetrahedron Lett. 2014,
55, 5443; e) B. Li, Y. Li, L. Yu, X. Wu, W. Wei, Tetrahedron 2017, 73,
2760.
[10] For selected examples, see: a) B. Du, P. Qian, Y. Wang, H. Mei, J. Han,
Y. Pan, Org. Lett. 2016, 18, 4144; b) S. Liang, N.-W. Liu, G.
Manolikakes, Adv. Synth. Catal. 2016, 358, 159; c) W.-H. Rao, B.-F.
Shi, Org. Lett. 2015, 17, 2784; d) J. Liu, L. Yu, S. Zhuang, Q. Gui, X.
Chen, W. Wang, Z. Tan, Chem. Commun. 2015, 51, 6418; e) Y. Xu, P.
Liu, S.-L. Li, P. Sun, J. Org. Chem. 2015, 80, 1269; f) Z. Wu, H. Song,
X. Cui, C. Pi, W. Du, Y. Wu, Org. Lett. 2013, 15, 1270; g) O. Saidi, J.
Marafie, A. E. W. Ledger, P. M. Liu, M. F. Mahon, G. Kociok-Köhn, M.
K. Whittlesey, C. G. Frost, J. Am. Chem. Soc. 2011, 133, 19298; h) X.
Zhao, E. Dimitrijevic, V. M. Dong, J. Am. Chem. Soc. 2009, 131, 3466.
[11] B. G. Szczepankiewicz, C. Kosogof, L. T. J. Nelson, G. Liu, B. Liu, H. Y.
Zhao, M. D. Serby, Z. L. Xin, M. Liu, R. J. Gum, D. L. Haasch, S. Y.
Wang, J. E. Clampit, E. F. Johnson, T. H. Lubben, M. A. Stashko, E. T.
Olejniczak, C. H. Sun, S. A. Dorwin, K. Haskins, C. Abad-Zapatero, E.
H. Fry, C. W. Hutchins, H. L. Sham, C. M. Rondinone, J. M. Trevillyan,
J. Med. Chem. 2006, 49, 3563.
[17] N.-W. Liu, S. Liang, G. Manolikakes, Adv. Synth. Cat. 2017, 359, 1308.
[18] a) S. Liang, M. Bolte, G. Manolikakes, Chem. Eur. J. 2017, 23, 96; b) S.
Liang, G. Manolikakes, Adv. Synth. Cat. 2016, 358, 2371.
[19] For the role of HFIP in oxidative transformation and the stabilization of
radical intermediates, see: a) B. Elsler, A. Wiebe, D. Schollmeyer, K. M.
Dyballa, R. Franke, S. R. Waldvogel, Chem. Eur. J. 2015, 21, 12321; b)
A. Berkessel, J. A. Adrio, J. Am. Chem. Soc. 2006, 128, 13412; c) L.
Eberson, O. Persson, M. P. Hartshorn, Angew. Chem. Int. Ed. 1995, 34,
2268.
[20] For the role of Mn(OAc)3 in oxidative radical reaction, see: B. B. Snider,
Chem. Rev. 1996, 96, 339.
[12] Marek K, Andrzej S, Krzysztof L, Jerzy P. PCT Int Appl. (2011), WO
2011009826 A2 20110127.
[21] Y. Kita, H. Tohma, K. Hatanaka, T. Takada, S. Fujita, S. Mitoh, H.
Sakurai, S. Oka, J. Am. Chem. Soc. 1994, 116, 3684.
[13] A. Kamimura, T. Nokubi, R. Watanabe, M. Ishikawa, K. Nasu, H. Uno,
M. Sumimoto, J. Org. Chem. 2014, 79, 1068.
[22] In most cases no reaction (except slow decomposition of the sulfinates)
was observed and the arene 1 was recovered completely. For 1h and
1i decomposition of the arene and a complex mixture of products was
observed.
[14] a) Y. Ogata, Y. Sawaki, M. Isono, Tetrahedron 1969, 25, 2715; b) J. M.
Bruce, P. Lloyd-Williams, J. Chem. Soc. Perkin Trans. 1 1992, 21,
2877; c) D. E. Allgeier, S. A. Herbert, R. Nee, K. D. Schlecht, K. T.
Finley, J. Org. Chem. 2003, 68, 4988.
[15]
a) D. O. Jang, K. S. Moon, D. H. Cho, J.-G. Kim, Tetrahedron Lett.
2006, 47, 6063; b) R. G. de Noronha, A. C. Fernandes, C. R. Romao,
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10.1002/ejoc.201700713
European Journal of Organic Chemistry
COMMUNICATION
COMMUNICATION
MeO
MeO
MeO
MeO
O O
S
A cross-dehyrogenative coupling of
1,4-dimethoxybenzenes with sodium
and lithium sulfinates is reported.
The reaction is mediated by
Mn(OAc)3 and provides various
arylsulfones in high yields.
C-H-Functionalization*
H
R SO2Met
R
Shuai Liang, Yueling Ren, Georg
Manolikakes
Mn(OAc)3
HFIP
25 °C, 2h
Page No. – Page No.
Mn-mediated C-H-functionalization
> 15 examples, 52-92% yield
Mn(OAc)3-Mediated C-H-
Sulfonylation of 1,4-
Dimethoxybenzenes with Sodium
and Lithium Sulfinates
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