Chemistry - A European Journal
10.1002/chem.201605101
COMMUNICATION
a)
8a
[
3]
J. Aziz, S. Messaoudi, M. Alami, A. Hamze, Org. Biomol. Chem. 2014,
Cu(OAc)2 (20 mol %)
Mn(OAc)3 (3.0 equiv.)
O
S
R
O
1
2, 9743.
SO2
NH
PA
R
Li
R
SO2Li
[4]
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,
-
40 to 25 °C
NaOAc (3.0 equiv)
HFIP, 25 °C, 90 min
1
0a (R = Ph)
11a (R = Ph)
11b (R = n-Bu)
9h: 73% (R = Ph)
9i: 62% (R =n-Bu)
1
0b (R = n-Bu)
1
5, 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.
b)
5a
I
SO Li
2
Cu(OAc)2 (20 mol %)
Mn(OAc)3 (4.0 equiv.)
1
) n-BuLi
0
°C
) SO2
40 °C
Ts
NH
IQA
[5]
2
NaOAc (3.0 equiv)
HFIP, 60 °C, 90 min
-
Me
Me
1
2
11c
7a: 71%
[
6]
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, 188.
c)
PA
8
a
HN
OMe
OMe
Cu(OAc)2 (20 mol %)
Mn(OAc)3 (3.0 equiv.)
1
) n-BuLi
SO2Li
OMe
0
°C
OMe
2
) SO2
NaOAc (3.0 equiv)
HFIP, 25 °C, 90 min
OMe
-
40 °C
S O
O
OMe
9j: 45%
1
3
11d
[
[
7]
8|
For reviews on C-H-activation, see: a) J. Liu, G. Chen, Z. Tan, Adv.
Synth. Catal., 2016, 358, 1174; b) T. Gensch, M. N. Hopkinson, F.
Glorius, J. Wencel-Delord, Chem. Soc. Rev. 2016, 45, 2900; c) C.
Shen, P. Zhang, Q. Sun, S. Bai, T. S. A. Hor, X. Liu, Chem. Soc. Rev.
Scheme 7. Synthesis and oxidative coupling of lithium sulfinates. Yields of
isolated products are given. IQA
picolinamide..
= 1-Isoquinolinecarboxamide. PA =
2
015, 44, 291; d) L. Ackermann, Chem. Rev. 2011, 111, 1315;
a) B. Du, P. Qian, Y. Wang, H. Mei, J. Han, Y. Pan, Org. Lett. 2016, 18,
4
3
144; b) S. Liang, N.-W. Liu, G. Manolikakes, Adv. Synth. Catal. 2016,
58, 159; c) W.-H. Rao, B.-F. Shi, Org. Lett. 2015, 17, 2784; d) J. Liu,
In summary, we have developed para-selective, cross-
dehydrogenative coupling of anilines with sulfinic acid salts. This
efficient, remote C-H functionalization could be achieved by a
L. Yu, S. Zhuang, Q. Gui, X. Chen, W. Wang, Z. Tan, Chem. Commun.
015, 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.
013, 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.
2
2
cooperative reaction system consisting of Cu(OAc)
2
as catalyst
and Mn(OAc) as oxidant in combination with the 1-isocuinoline
3
carboxamide directing group. This system overrides the usual
ortho-selectivity of directing group-assisted copper-catalyzed
C-H functionalizations. The reaction conditions are quite mild
and tolerate range of functional groups. Moreover we could
show, that, through the combination of organolithium chemistry
and the oxidative C-H sulfonylation, a variety of interesting
arylsulfones is accessible from simple building blocks. Although
[
9|
a) A. Dey, S. Maity, D. Maiti, Chem. Commun. 2016, 52, 12398; b) L.
Ackermann, J. Li, Nature Chem. 2015, 7, 686.
[10] for selected examples, see: a) N. Y. P. Kumar, A. Bechtoldt, K.
Raghuvanshi, L. Ackermann, Angew. Chem. Int. Ed. 2016, 55, 6929; b)
T. Patra, S. Bag, R. Kancherla, A. Mondal, A. Dey, S. Pimparkar, S.
Agasti, A. Modak, D. Maiti, Angew. Chem. Int. Ed. 2016, 55, 7751; c) Y.
Kuninobu, H. Ida, M. Nishi, M. Kanai, Nature Chem. 2015, 7, 712; d) X.-
C. Wang, W. Gong, L.-Z. Fang, R.-Y. Zhu, S. Li, K. M. Engle, J.-Q. Yu,
Nature 2015, 519, 334 and references therein.
[11] a) S. Liang, G. Manolikakes, Adv. Synth. Cat. 2016, 358, 2371; b) C.
Xia, K. Wang, J. Xu, Z. Wei, C. Shen, G. Duan, Q. Zhu, P. Zhang, RSC
Adv. 2016, 6,37173; c) J. Wei, J. Jiang, X. Xiao, D. Lin, Y. Deng, Z. Ke,
H. Jiang, W. Zeng, J. Org. Chem. 2016, 81, 946; d) H.-W.Liang, K.
Jiang, W. Ding, Y. Yuan, L. Shuai, Y.-C.Chen, Y. Wei, Chem. Commun.
[
18]
the reaction mechanism is not clarified so far,
our approach
offers a new opportunity for copper-catalyzed para-selective
oxidative C-H functionalization of arenes. Application of our
concept in other cross-dehydrogenative couplings is currently
under investigation in our laboratory.
2
015, 51, 16928; f) H. Qiao, S. Sun, F. Yang, Y.Zhu, W. Zhu, Y. Dong,
Y. Wu,X.Kong, L. Jiang, Y. Wu, Org. Lett. 2015, 17, 6086.
|
12] A. M. Suess, M. Z. Ertem, C. J. Cramer, S. S. Stahl, J. Am. Chem. Soc.
2
013, 135, 9797.
[
13] Most copper-catalyzed C-H-functionalizations proceed ortho-selective;
see ref 7. For some rare examples of copper-catalyzed meta- and para-
selective C-H-functionalizations, see: a) B. Berzina, I. Sokolovs, E.
Suna, ACS Catal. 2015, 5, 7008; b) H. A. Duong, R. E. Gilligan, M. L.
Cooke, R. J. Phipps, M. J. Gaunt, Angew. Chem. Int. Ed. 2011, 50, 463;
c) R. J. Phipps, M. J. Gaunt, Science, 2009, 323, 1593.
Acknowledgements
Financial support by the Fonds der Chemischen Industrie (Liebig
Fellowship to G.M.), the Boehringer Ingelheim Foundation
[
[
14] The structures of 7a, 7t, 9a and 9e were assigned via single crystal x-
(
(
Exploration Grant to G. M.) and China Scholarships Council
PhD fellowship to S. L.) is gratefully acknowledged. We would
ray diffraction. CCDC files 1509039-1509042
contain the
supplementary crystallographic data for this paper and can be obtained
free of charge from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
like to thank Prof. Michael Göbel (Goethe-University Frankfurt)
for his support, and Rockwood Lithium GmbH (Frankfurt) for the
generous donation of chemicals.
15] 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.
Keywords: sulfone • C-H functionalization • copper •
manganese • site-selectivity
[
[
16] Use of the Isochinolincarboxamide directing group does not lead to a
significant increase in yield (typically 5%).
17] J. Clayden, Organolithiums: Selectivity for Synthesis, Pergamon Press,
Oxford, 2002.
[
[
1]
2]
a) S. Patai, C. Z. Rappoport, J. M. Strirling, The Chemistry of Sulfones
and Sulfoxides, Wiley, New York, 1988; b) N. S. Simpkins, Sulphones
in Organic Synthesis, Pergamon Press, Oxford, 1993.
[18] See the SI for preliminary mechanistic investigations.
N.-W. Liu, S. Liang, G. Manolikakes, Synthesis 2016, 1939.
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