Angewandte Chemie International Edition
10.1002/anie.202002717
COMMUNICATION
[
[
1]
2]
a) A. Sudalai, A. Khenkin, R. Neumann, Org. Biomol. Chem. 2015, 13,
commercially derived materials (Fig. S16 in SI), being in good
accordance with the Bio-Rad database.[40] Furthermore, the
electrochemically synthesized meta-periodate was tested in the
sulfide and the Malaprade oxidation (Scheme 3). This
performance was also compared to commercial meta-
periodate.[41] In both oxidations, full conversion was achieved
with both, the synthesized and the commercial meta-periodate,
confirming the high quality of the periodate generated by this
electrochemical method.
4374–4394; b) P. L. Fuchs, A. B. Charette, T. Rovis, J. W. Bode,
Essential Reagents for Organic Synthesis, Wiley, Weinheim, 2016.
a) M. Abdel-Akher, F. Smith, J. Am. Chem. Soc. 1959, 81, 1718–1721;
b) E. L. Jackson, C. S. Hudson, J. Am. Chem. Soc. 1939, 61, 959–960;
c) B. Sklarz, Q. Rev. Chem. Soc. 1967, 21, 3; d) M. Zhou, R. H.
Crabtree, Chem. Soc. Rev. 2011, 40, 1875–1884; e) B. Plietker,
Synthesis 2005, 2453–2472.
[
[
3]
4]
a) L. Kraszkiewicz, M. Sosnowski, L. Skulski, Synthesis 2006, 1195–
1199; b) P. Chouthaiwale, P. Karabal, G. Suryavanshi, A. Sudalai,
Synthesis 2010, 3879–3882.
J. M. Murphy, C. C. Tzschucke, J. F. Hartwig, Org. Lett. 2007, 9, 757–
760.
[
[
5]
6]
P. I. Kitov, D. R. Bundle, Org. Lett. 2001, 3, 2835–2838.
a) Y. K. Chen, A. E. Lurain, P. J. Walsh, J. Am. Chem. Soc. 2002, 124,
12225–12231; b) C. Palomo, M. Oiarbide, R. Halder, M. Kelso, E.
Gómez-Bengoa, J. M. García, J. Am. Chem. Soc. 2004, 126, 9188–
9189; c) K. Juhl, K. A. Jørgensen, J. Am. Chem. Soc. 2002, 124, 2420–
2421.
[
[
7]
8]
a) B. Das, M. Lingaiah, K. Damodar, N. Bhunia, Synthesis 2011, 2941–
944; b) J. M. Smith, J. A. Dixon, J. N. deGruyter, P. S. Baran, J. Med.
Chem. 2019, 62, 2256–2264.
2
a) K. Satyanarayana, K. Srinivas, V. Himabindu, G. M. Reddy, Org.
Process Res. Dev. 2007, 11, 842–845; b) X. Wang, Y. Zeng, L. Sheng,
P. Larson, X. Liu, X. Zou, S. Wang, K. Guo, C. Ma, G. Zhang et al., J.
Med. Chem. 2019, 62, 2305–2332; c) S. Zhou, Y. Jia, Org. Lett. 2014,
16, 3416–3418; d) X. Gao, S. K. Woo, M. J. Krische, J. Am. Chem. Soc.
2013, 135, 4223–4226; e) F. Bihelovic, R. N. Saicic, Angew. Chem. Int.
Ed. 2012, 51, 5687–5691; Angew. Chem. 2012, 124, 5785–5789.
Molar costs were calculated based on the best price offers from Sigma
Aldrich/Merck KGaA. https://www.sigmaaldrich.com/germany.html,
Scheme 3: Synthetic confirmation of the electrochemically synthesized meta-
periodate. Yields were determined by 1H NMR spectroscopy versus caffeine
as internal standard. All reactions showed full conversion of the starting
material.
[9]
2
019.
10] a) J. Röckl, D. Pollok, R. Franke, S. R. Waldvogel, Acc. Chem. Res.
020, 53, 45–61; b) A. Wiebe, T. Gieshoff, S. Möhle, E. Rodrigo, M.
In summary, the direct electrochemical synthesis of
periodate from common iodides has been established at a BDD
anode. The conventional use of non-durable metal-based
electrodes, in particular lead dioxide, was hereby avoided, which
prevents contamination and enables the use of periodate in
sensitive applications. In contrast to previous reports, the total
number of synthetic steps was reduced by starting from iodide,
therefore allowing a simple, robust and cost-efficient synthesis.
The conditions have been optimized by statistical experiments
where the optimal stoichiometry of hydroxide to iodide was
determined to 10:1. The current density had only a small effect
on the yield allowing the application of low current densities
[
2
Zirbes, S. R. Waldvogel, Angew. Chem. Int. Ed. 2018, 57, 5594–5619;
Angew. Chem. 2018, 130, 5694–5721; c) A. Wiebe, T. Gieshoff, S.
Möhle, E. Rodrigo, M. Zirbes, S. R. Waldvogel, Angew. Chem. Int. Ed.
2
018, 57, 6018–6041; Angew. Chem. 2018, 130, 5694–5721; d) S. R.
Waldvogel, S. Lips, M. Selt, B. Riehl, C. J. Kampf, Chem. Rev. 2018,
18, 6706–6765.
1
[11] a) R. Francke, Curr. Opin. Electrochem. 2019, 15, 83–88; b) J. D.
Haupt, M. Berger, S. R. Waldvogel, Org. Lett. 2019, 21, 242–245; c) J.
D. Herszman, M. Berger, S. R. Waldvogel, Org. Lett. 2019, 21, 19,
7
1
893–7896; d) R. Möckel, E. Babaoglu, G. Hilt, Chem. Eur. J. 2018, 24,
5781–15785; e) M. Elsherbini, T. Wirth, Chem. Eur. J. 2018, 24,
13399–13407; f) M. Elsherbini, B. Winterson, H. Alharbi, A. A.
Folgueiras, A. C. Génot, T. Wirth, Angew. Chem. Int. Ed. 2019, 58,
2
below 500 mA/cm . At such, the heat generation is moderate,
which contributes to an energy efficient process and a yield of
9811-9815; Angew. Chem. 2019, 131, 9916–9920.
[
12] a) Y. Xia, Q. Dai, J. Chen, J. Electroanal. Chem. 2015, 744, 117–125;
94%. The synthesis was scaled-up to 100 g para-periodate in a
b) J. K. Kim, B. S. Choi, C. W. Nam, Kongop Hwahak 1996, 7, 1105–
flow-electrolysis cell enhancing the space-time yields in a
cyclization protocol. This electrochemical approach will propel
periodate to a more used oxidizer in several fields wherein toxic
heavy metals are considered to be critical. Furthermore, a novel
analysis method was developed based on high performance
liquid chromatography, which enables the time- and material-
efficient determination of periodate along with iodate and iodine.
This method will accelerate the future research in the field of
hypervalent iodic species.
1
114.
[13] a) Y.-s. Wang, F. Yang, Z.-h. Liu, L. Yuan, G. Li, Catal. Commun. 2015,
67, 49–53; b) A. Mukimin, H. Vistanty, N. Zen, Chem. Eng. J. 2015, 259,
430–437.
[
14] Y. Aiya, S. Fujii, K. Sugino, K. Shirai, J. Electrochem. Soc. 1962, 109,
19–424.
15] C. L. Mehltretter, US2830941A, 1958.
4
[
[16] a) European Medicines Agency, ICH guideline Q3D (R1) on elemental
impurities, can be found under https://www.ich.org/page/quality-
guidelines, 2019; b) D. R. Abernethy, A. J. Destefano, T. L. Cecil, K.
Zaidi, R. L. Williams, Pharm. Res. 2010, 27, 750–755.
[
[
[
17] A. Hickling, S. H. Richards, J. Chem. Soc. 1940, 256–264.
18] E. Müller, Z. Elektrochem. 1901, 38, 509–517.
19] a) E. Müller, Z. Elektrochem. 1904, 4, 51–68; b) D. Kong, P. Wan, Y.
Chen, Z. U. l. H. Khan, Y. Tang, Int. J. Electrochem. Sci. 2015, 6422–
Acknowledgements
6432; c) Y. Gan, B. Yao, W. Zhang, H. Huang, Y. Xia, J. Zhang, C.
Funded by the Deutsche Forschungsgemeinschaft (DFG,
German Research Foundation in frame of FOR 2982 - UNDODE
Wa1276/23-1).
Liang, X. He, CN 110158112, 2019.
[
[
[
20] C. W. Nam, H. J. Kim, J. Korean Chem. Soc. 1974, 18, 373–380.
21] K. Hirakata, M. Mochizuki, H. Kanai, R. Itai, US4687565A, 1987.
22] H. H. Willard, R. R. Ralston, Trans. Electrochem. Soc. 1932, 62, 239–
2
54.
[23] a) C. W. Nam, H. J. Kim, J. Korean Chem. Soc. 1971, 15, 324–329.
24] a) S. R. Waldvogel, S. Mentizi, A. Kirste, Top. Curr. Chem. 2012, 320,
–31; b) N. Yang, S. Yu, J. V. Macpherson, Y. Einaga, H. Zhao, G.
Keywords: Oxidation • Electrolysis • Synthesis • Periodate •
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Boron-doped diamond
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