Please do not adjust margins
ChemComm
Page 4 of 5
COMMUNICATION
Journal Name
5
6
ACS Catal., 2018, 8, 7727.
K. M.K. Kutterer, J. M. Davis, G. Singh,DYO. YI:a1n0g.1,0W39./DH0uC,CA0.1052A
Severin, B. A. Rasmussen, G. Krishnamurthy, A. Failli and A.
H. Katz, Bioorg. Med. Chem. Lett., 2005, 15, 2527; A. M.
Gilbert, A. Failli, J. Shumsky, Y. Yang, A. Severin, G. Singh, W.
Hu, D. Keeney, P. J. Petersen and A. H. Katz, J. Med. Chem.,
2006, 49, 6027; A. M. Khalil, M. A. Berghot, M. A. Gouda and
S. A. El Bialy, Monatsh. Chem., 2010, 141, 1353; US Pat.,
US2562830 A, 1949; R. G. Child, A. C. Osterberg, A. E.
Sloboda and A. S. Tomcufcik, J. Pharm. Sci., 1977, 66, 466; F.
Al'‐Assar, K. N. Zelenin, E. E. Lesiovskaya, I. P. Bezhan and B.
A. Chakchir, Pharm. Chem. J., 2002, 36, 598.
N. M. Przheval'skii, I. V. Magedov and V. N. Drozd, Synthesis,
1993, 1993, 463; J. A. S. Luis, T. M. de Aquino, B. F. Lira, P. F.
A. Filho, M. T. Scotti, L. Scotti, R. O. de Moura and F. J. B. M.
Junior, Acta Pharm., 2014, 64, 233.
C. Frauches-Santos, G. F. Bauerfeldt and A. Echevarria, Int. J.
Electrochem. Sci., 2018, 13, 6978.
7
8
9
Vogel’s Textbook of Practical Organic Chemistry, ed. B. S.
Furniss, A. J. Hannaford, P. W. G. Smith and A. R. Tatchell,
Pearson Education Limited, London, 5th edn., 1989; F. A.
Kahn, J. Dash, C. Sudheer and R.K. Gupta, Tetrahedron Lett.,
2003, 44, 7783.
10 J. Chen, Y. Zhang, W. Hao, R. Zhang and F. Yi, Tetrahedron,
2013, 69, 613; Z. Wang, R. T. Skerlj and G. J. Bridger,
Tetrahedron Lett., 1999, 40, 3543; A. Samzadeh-Kermani,
Tetrahedron Lett., 2016, 57, 463; H.-M. Kang, Y.-K. Lim, I.-J.
Shin, H.-Y. Kim and C.-G. Cho, Synfacts, 2006, 2006, 781.
11 G. Boche, R. H. Reinhard and F. Bosold, Angew. Chem. Int.
Ed., 1986, 25, 562.
12 O. Loog, U. Mäeorg and U. Ragnarsson, Synthesis, 2000,
2000, 1591; O. Loog and U. Mäeorg, Synlett, 2004, 2004,
2537.
13 S. Möhle, M. Zirbes, E. Rodrigo, T. Gieshoff, A. Wiebe and S.
R. Waldvogel, Angew. Chem. Int. Ed., 2018, 57, 6018; A.
Wiebe, T. Gieshoff, S. Möhle, E. Rodrigo, M. Zirbes and S. R.
Waldvogel, Angew. Chem. Int. Ed., 2018, 57, 5594; S. R.
Waldvogel, S. Lips, M. Selt, B. Riehl and C. J. Kampf, Chem.
Rev., 2018, 118, 6706; M. Yan, Y. Kawanata and P. S. Baran,
Chem. Rev., 2017, 117, 13230; E. J. Horn, B. R. Rosen and P.
S. Baran, ACS Cent. Sci., 2016, 2, 302.
14 B. A. Frontana-Uribe, R. D. Little, J. G. Ibanez, A. Palma and R.
Vasquez-Medrano, Green Chem., 2010, 12, 2099; S. R.
Waldvogel, Beilstein J. Org. Chem., 2015, 11, 949; H.-J.
Schäfer, C. R. Chim., 2011, 14, 745.
Scheme 5: Parameter controlled C-C (blue, 5), N-N (green, 2) dimerization or
benzoxazole-formation (red, 6) of protected anilides 1.16,22
accomplished by using HFIP and tetrabutylammonium hexafluo-
rophosphate as electrolyte with isostatic graphite as anode
(red).16
In summary, we established an electrochemical access to pro-
tected hydrazine derivatives, by dehydrogenative anodic oxida-
tion of anilides. The presented synthetic reaction pathway pro-
vides a reagent-free, sustainable, and favorable alternative to
conventional synthetic protocols using easily accessible and in-
expensive anilide derivatives as starting materials. A broad vari-
ety of substituents of electron withdrawing, labile moieties,
multiple substituted aromatic systems, and different protecting
groups have been successfully converted in yields up to 66%. In
order to enable further modifications halide and cyano moieties
could are tolerated. Furthermore, the scalability of the reaction
and the deprotection have been demonstrated (derivative 2a).
15 T. Gieshoff, A. Kehl, D. Schollmeyer, K. D. Moeller and S. R.
Waldvogel, J. Am. Chem. Soc., 2017, 139, 12317.
16 T. Gieshoff, A. Kehl, D. Schollmeyer, K. D. Moeller and S. R.
Waldvogel, Chem. Commun., 2017, 53, 2974.
17 T. Gieshoff, D. Schollmeyer and S. R. Waldvogel, Angew.
Chem. Int. Ed., 2016, 55, 9437; A. Kehl, T. Gieshoff, D.
Schollmeyer and S. R. Waldvogel, Chem. - Eur. J., 2018, 24,
590.
18 A. Kehl, V. M. Breising, D. Schollmeyer and S. R. Waldvogel,
Chem. Eur. J., 2018, 24, 17230.
19 B. R. Rosen, E. W. Werner, A. G. O'Brien and P. S. Baran, J.
Am. Chem. Soc., 2014, 136, 5571.
20 A. Shrestha, M. Lee, A. L. Dunn and M. S. Sanford, Org. Let.,
2018, 20, 204.
21 C. Gütz, B. Klöckner and S. R. Waldvogel, Org. Process Res.
Dev., 2016, 20, 26.
22 L. Schulz, M. Enders, B. Elsler, D. Schollmeyer, K. M. Dyballa,
R. Franke and S. R. Waldvogel, Angew. Chem. Int. Ed., 2017,
56, 4877; L. Schulz, R. Franke and S. R. Waldvogel,
ChemElectroChem, 2018, 5, 2069; L. Schulz, J.-A. Husmann
and S. R. Waldvogel, Electrochim. Acta, 2020, 337, 135786.
Conflicts of interest
There are no conflicts to declare.
Notes and references
§ S.R.W. gratefully acknowledges financial support by the DFG
(Wa 1276/17-2).
1
2
3
4
J.-Y. Kim, D.-H. Kim, T.-H. Jeon, W.-H. Kim and C.-G. Cho, Org.
Lett., 2017, 19, 4688.
K. Hunger, P. Mischke and W. Rieper, in Ullmann's
encyclopedia of industrial chemistry, Wiley, Chichester, 2010.
N. Zinin, J. Prakt. Chem., 1845, 36, 93; H. Schmidt and G.
Schultz, Justus Liebigs Ann. Chem., 1881, 207, 320.
Z. Yang, S. Hou, W. He, B. Cheng, P. Jiao and J. Xu,
Tetrahedron, 2016, 72, 2186; S. Hou, X. Li and J. Xu, Org.
Biomol. Chem., 2014, 12, 4952; J. Xu, Curr. Org. Synth., 2017,
14, 511.
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins