Pyrazoles in the Intersection of Mesomeric Betaines and N-Heterocyclic Carbenes: Formation of NHC Selenium Adducts of Pyrazolium-4-aminides

Kai Hillrichs; Jan C. Namyslo; Felix Lederle; Eike G. Hübner; Andreas Schmidt

doi:10.1055/s-0040-1719912

Synthesis, Table of Contents

Synthesis 2022; 54(15): 3351-3366
DOI: 10.1055/s-0040-1719912

feature

Pyrazoles in the Intersection of Mesomeric Betaines and N-Heterocyclic Carbenes: Formation of NHC Selenium Adducts of Pyrazolium-4-aminides

Kai Hillrichs

^aClausthal University of Technology, Institute of Organic Chemistry, Leibnizstrasse 6, 38678 Clausthal-Zellerfeld, Germany

,

Jan C. Namyslo

^aClausthal University of Technology, Institute of Organic Chemistry, Leibnizstrasse 6, 38678 Clausthal-Zellerfeld, Germany

,

Felix Lederle

^bFraunhofer Heinrich Hertz Institute HHI, Fiber Optical Sensor Systems, Am Stollen 19 H, 38640 Goslar, Germany

,

Eike G. Hübner

^aClausthal University of Technology, Institute of Organic Chemistry, Leibnizstrasse 6, 38678 Clausthal-Zellerfeld, Germany

^bFraunhofer Heinrich Hertz Institute HHI, Fiber Optical Sensor Systems, Am Stollen 19 H, 38640 Goslar, Germany

,

Andreas Schmidt ∗

^aClausthal University of Technology, Institute of Organic Chemistry, Leibnizstrasse 6, 38678 Clausthal-Zellerfeld, Germany

› Author Affiliations

Abstract

All articles of this category

Abstract

Starting from 4-nitropyrazole, eight mesoionic pyrazolium-4-aminides were prepared by a six-step reaction sequence. The deprotonation of 1,2-disubstituted 4-amido-1H-pyrazolium salts by an anion exchange resin in its hydroxide form is the final step of the synthesis. A tautomeric equilibrium between the mesoionic compounds (pyrazolium-4-aminides) and N-heterocyclic carbenes (pyrazol-3-ylidenes) can be formulated; however, the NHC tautomers were not detected by means of NMR spectroscopy in polar aprotic solvents such as DMSO-d ₆ or MeCN-d ₃. Apart from tautomerism, anionic N-heterocyclic carbenes can be formulated as a result of a deprotonation of the mesoionic compounds. Trapping reactions were performed with selenium, which resulted in the formation of pyrazole-3-selenones. Methylation at the selenium atom gave the corresponding 3-(methylselanyl)-4-amido-1H-pyrazolium salts, which were deprotonated to give new mesomeric betaines, 3-(methylselanyl)-1H-pyrazolium-4-aminides as unique compounds. DFT-calculations as well as ⁷⁷Se NMR spectroscopic measurements were carried out.

Key words

pyrazol-3-ylidenes - mesoionic compound - pyrazol-3-selenone - selenium ether - ⁷⁷Se NMR - selone - mesoionic imine

Full Text

References

References
1 Böttinger C. Justus Liebigs Ann. Chem. 1881; 208: 122
2 Breslow R. J. Am. Chem. Soc. 1958; 80: 3719
3 Brown BR, Hammick DL. J. Chem. Soc. 1949; 659

4a Quast H, Frankenfeld E. Angew. Chem., Int. Ed. Engl. 1965; 4: 691
4b Quast H, Schmitt E. Justus Liebigs Ann. Chem. 1970; 732: 43

5 Katritzky AR, Awartani R, Patel RC. J. Org. Chem. 1982; 47: 498

6a Haake P, Bausher LP. J. Phys. Chem. 1968; 72: 2213
6b Maier G, Endres J. Eur. J. Org. Chem. 1998; 1517
6c Van Ausdall BR, Glass JL, Wiggins KM, Aarif AM, Louie J. J. Org. Chem. 2009; 74: 7935
6d Zhou H, Zhang W.-Z, Liu C.-H, Qu J.-P, Lu X.-B. J. Org. Chem. 2008; 73: 8039

7 Breslow R. J. Am. Chem. Soc. 1958; 80: 3719

8a Wanzlick H.-W, Schikora E. Angew. Chem. 1960; 72: 494
8b Wanzlick H.-W, Lachmann B, Schikora E. Chem. Ber. 1965; 98: 3170
8c Öfele K. J. Organomet. Chem. 1968; 12: P42

9 Arduengo AJ, Harlow RL, Kline M. J. Am. Chem. Soc. 1991; 113: 361

10a N-Heterocyclic Carbenes in Organocatalysis . Biju AT. Wiley-VCH; Weinheim: 2019
10b N-Heterocyclic Carbenes: Effective Tools for Organometallic Synthesis. Nolan SP. Wiley-VCH; Weinheim: 2014
10c Science of Synthesis: N-Heterocyclic Carbenes in Catalytic Organic Synthesis. Nolan SP, Cazin CS. J. Thieme Verlag; Stuttgart: 2017
10d N-Heterocyclic Carbenes in Transition Metal Catalysis. In Topics in Organometallic Chemistry, Vol. 21. Glorius F. Springer; Berlin: 2010
10e Merceron-Saffon N, Baceiredo A, Gornitzka H, Bertrand G. Science 2003; 301: 1223
10f Hahn FE, Jahnke MC. Angew. Chem. Int. Ed. 2008; 47: 3122
10g Budagumpi S, Haque RA, Endud S, Rehman GU, Salman AW. Eur. J. Inorg. Chem. 2013; 4367
10h Hille C, Kühn FE. Dalton Trans. 2015; 15
10i Sandtorv AH, Leitch C, Bedringaas SL, Gjertsen BT, Bjørsvik H.-R. ChemMedChem 2015; 10: 1522
10j Nasr A, Winkler A, Tamm M. Coord. Chem. Rev. 2016; 316: 68
10k Ezugwu CI, Kabir NA, Yusubov M, Verpoort F. Coord. Chem. Rev. 2016; 307: 188
10l Ohki Y, Seino H. Dalton Trans. 2016; 874
10m Ritleng V, Henrion M, Chetcuti MJ. ACS Catal. 2016; 890

11 Doddi A, Peters M, Tamm M. Chem. Rev. 2019; 119: 6994
12 Danopoulos AA, Simler T, Braunstein P. Chem. Rev. 2019; 119: 3730
13 Schmidt A, Wiechmann S, Otto CF. Adv. Heterocycl. Chem. 2016; 119: 143

14a Siemeling U, Memczak H, Bruhn C, Vogel F, Träger F, Baio JE, Weidner T. Dalton Trans. 2012; 2986
14b Korotkikh NI, Saberov VSh, Kiselev AV, Glinyanaya NV, Marichev KA, Pekhtereva TM, Dudarenko GV, Bumagin NA, Shvaika OP. Chem. Heterocycl. Compd. 2012; 47: 1551
14c Bittermann A, Baskakov D, Herrmann WA. Organometallics 2009; 28: 5107

15 Kuhn N, Kratz T. Synthesis 1993; 561

16a Medici F, Gontard G, Derat E, Lemière G, Fensterbank L. Organometallics 2018; 37: 517
16b Hetterscheid DG. H, Reek JN. H. Chem. Commun. 2011; 47: 2712
16c Cesari C, Cingolani A, Teti M, Messori A, Zacchini S, Zanotti V, Mazzoni R. Eur. J. Inorg. Chem. 2020; 1114

17a Li W, Tang J, Li S, Zheng X, Yuan M, Xu B, Jiang W, Fu H, Li R, Chen H. Org. Lett. 2020; 22: 7814
17b Prades A, Viciano M, Sanau M, Peris E. Organometallics 2008; 27: 4254
17c Tafipolsky M, Scherer W, Öfele K, Artus G, Pedersen B, Herrmann WA, McGrady GS. J. Am. Chem. Soc. 2002; 124: 5865
17d Schütz J, Herdtweck E, Herrmann WA. Organometallics 2004; 23: 6084

18 Schmidt A, Guan Z. Synthesis 2012; 3251
19 Schmidt A, Wiechmann S, Freese T. ARKIVOC 2013; (i): 424

20a Nylund PV. S, Ségaud NC, Albrecht M. Organometallics 2021; 40: 1538
20b Lee E, Lee J, Yandulov DV. Eur. J. Inorg. Chem. 2017; 2058
20c Ségaud N, McMaster J, van Koten G, Albrecht M. Inorg. Chem. 2019; 58: 16047
20d Ainembabazi D, Wang K, Finn M, Ridenour J, Voutchkova-Kostal A. Green Chem. 2020; 22: 6093
20e Filonenko GA, Lugger JA. M, Liu C, van Heeswijk EP. A, Hendrix MM. R. M, Weber M, Müller C, Hensen EJ. M, Sijbesma RP, Pidko EA. Angew. Chem. Int. Ed. 2018; 57: 16385
20f Roselló-Merino M, Díez J, Conejero S. Chem. Commun. 2010; 46: 9247

21a Färber C, Leibold M, Bruhn C, Maurer M, Siemeling U. Chem. Commun. 2012; 227
21b César V, Tourneux J.-C, Vujkovic N, Brousses R, Lugan N, Lavigne G. Chem. Commun. 2012; 48: 2349
21c Danopoulos AA, Monakhov KYu, Braunstein P. Chem. Eur. J. 2013; 19: 450

22a César V, Mallardo V, Nano A, Dahm G, Lugan N, Lavigne G, Bellemin-Laponnaz S. Chem. Commun. 2015; 51: 5271
22b Benhamou L, Vujkovic N, César V, Gornitzka H, Lugan N, Lavigne G. Organometallics 2010; 29: 2616
22c Benhamou L, César V, Gornitzka H, Lugan N, Lavigne G. Chem. Commun. 2009; 4720
22d Biju AT, Hirano K, Fröhlich R, Glorius F. Chem. Asian J. 2009; 4: 1786
22e Pidlypnyi N, Uhrner F, Nieger M, Drafz MH. H, Hübner EG, Namyslo JC, Schmidt A. Eur. J. Org. Chem. 2013; 7739

23a Ramsden CA. Tetrahedron 2013; 69: 4146
23b Ramsden CA, Oziminski WP. Tetrahedron 2014; 70: 7158
23c Oziminski WP, Ramsden CA. Tetrahedron 2015; 71: 7191

24 Wiechmann S, Freese T, Drafz MH. H, Hübner EG, Namyslo JC, Nieger M, Schmidt A. Chem. Commun. 2014; 50: 11822

25a Freese T, Nieger M, Namyslo JC, Schmidt A. Tetrahedron Lett. 2019; 60: 1272
25b Freese T, Namyslo JC, Nieger M, Schmidt A. RSC Adv. 2019; 9: 4781
25c Freese T, Lücke A.-L, Namyslo JC, Nieger M, Schmidt A. Eur. J. Org. Chem. 2018; 1646
25d Freese T, Lücke A.-L, Schmidt CA. S, Polamo M, Nieger M, Namyslo JC, Schmidt A. Tetrahedron 2017; 73: 5350

26 Mummel S, Lederle F, Hübner EG, Namyslo JC, Nieger M, Schmidt A. Angew. Chem. Int. Ed. 2021; 60: 18882

27a Lavigne G, César V, Lugan N. Chem. Eur. J. 2010; 16: 11432
27b César V, Lugan N, Lavigne G. J. Am. Chem. Soc. 2008; 130: 11286

28a Schmidt A, Münster N, Dreger A. Angew. Chem. Int. Ed. 2010; 49: 2790
28b Schmidt A, Habeck T. Lett. Org. Chem. 2005; 2: 37

29a Ollis WD, Stanforth SP, Ramsden CA. Tetrahedron 1985; 41: 2239
29b Katritzky AR. Chem. Ind. 1955; 521

30a Schmidt A, Beutler A, Albrecht M, Ramírez FJ. Org. Biomol. Chem. 2008; 6: 287
30b Fèvre M, Pinaud J, Leteneur A, Gnanou Y, Vignolle J, Taton D, Miqueu K, Sotiropoulos J.-M. J. Am. Chem. Soc. 2012; 134: 6776
30c Sauvage X, Demonceau A, Delaude L. Adv. Synth. Catal. 2009; 351: 2031
30d Kolychev EL, Bannenberg T, Freytag M, Daniliuc CG, Jones PG, Tamm M. Chem. Eur. J. 2012; 18: 16938

31a Guan Z, Wiechmann S, Drafz M, Hübner E, Schmidt A. Org. Biomol. Chem. 2013; 11: 3558
31b Schmidt A, Merkel L, Eisfeld W. Eur. J. Org. Chem. 2005; 2124

32 Castells J, Calahorra FL, Domingo L. Tetrahedron Lett. 1985; 26: 5457
33 Dreger A, Nieger M, Drafz M, Schmidt A. Z. Naturforsch., B: J. Chem. Sci. 2012; 67: 359
34 Schmidt A, Nieger M. Heterocycles 1999; 51: 2119

35a Schmidt A, Snovydovych B, Hemmen S. Eur. J. Org. Chem. 2008; 4313
35b Schmidt A, Snovydovych B. Synthesis 2008; 2798
35c Schmidt A, Beutler A, Habeck T, Mordhorst T, Snovydovych B. Synthesis 2006; 1882

36 Schmidt A, Mordhorst T, Habeck T. Org. Lett. 2002; 4: 1375
37 Han SJ, Kim HT, Joo JM. J. Org. Chem. 2016; 81: 689
38 Liu J.-Q, Hao B.-Y, Zou H, Zhang W.-H, Chen X.-Z. ARKIVOC 2014; (v): 72
39 Zhang N, Sun Q, Wang T. UA Patent 336982, 2015
40 Deev S, Batsyts S, Sheina E, Shestakova TS, Khalimbadzha I, Kiskin MA, Charushin V, Chupakhin O, Paramonov AS, Shenkarev ZO, Namyslo JC, Schmidt A. Eur. J. Org. Chem. 2020; 450
41 Zhang J, Hübner EG, Namyslo JC, Nieger M, Schmidt A. Org. Biomol. Chem. 2018; 16: 6801

42a Liu M, Namyslo JC, Nieger M, Polamo M, Schmidt A. Beilstein J. Org. Chem. 2016; 12: 2673
42b Liu M, Nieger M, Hübner E, Schmidt A. Chem. Eur. J. 2016; 5416

43a Granovsky A. A.; Firefly version 8; http://classic.chem.msu.su/gran/firefly/index.html
43b Schmidt MW, Baldridge KK, Boatz JA, Elbert ST, Gordon MS, Jensen JH, Koseki S, Matsunaga N, Nguyen KA, Su S, Windus TL, Dupuis M, Montgomery JA. J. Comput. Chem. 1993; 14: 1347
43c Jmol, an open-source Java viewer for chemical structures in 3D (accessed Nov 2019): http://jmol.sourceforge.net/

44a Ramsden CA, Oziminski WP. J. Org. Chem. 2016; 81: 10295
44b Ramsden CA, Oziminski WP. J. Org. Chem. 2017; 82: 12485
44c Oziminski WP, Ramsden CA. RSC Adv. 2018; 8: 14833

45 Mathew J, Suresh CH. Inorg. Chem. 2010; 49: 4665
46 Perrin L, Clot E, Eisenstein O, Loch J, Crabtree RH. Inorg. Chem. 2001; 40: 5806
47 Tolman CA. J. Am. Chem. Soc. 1970; 92: 2953
48 Tukov AA, Normand AT, Nechaev MS. Dalton Trans. 2009; 7015
49 Bourissou D, Guerret O, Gabbaï FP, Bertrand G. Chem. Rev. 2000; 100: 39
50 Bernhammer JC, Frison G, Huynh HV. Chem. Eur. J. 2013; 19: 12892
51 Verlinden K, Buhl H, Frank W, Ganter C. Eur. J. Inorg. Chem. 2015; 2416

52a Huynh HV, Han Y, Jothibasu R, Yang JA. Organometallics 2009; 28: 5395
52b Teng Q, Huynh HV. Dalton Trans. 2017; 614

53 Huynh HV. Chem. Rev. 2018; 118: 9457

54a Review: Nasr A, Winkler A, Tamm M. Coord. Chem. Rev. 2016; 316: 68

Recent publications:

54b Frosch J, Koneczny M, Bannenberg T, Tamm M. Chem. Eur. J. 2021; 4349
54c Grineva AA, Valyaev DA, César V, Filippov OA, Khrustalev VN, Nefedov SE, Lugan N. Angew. Chem. Int. Ed. 2018; 57: 7986 ; Angew. Chem. 2018, 130, 8118
54d Medici F, Gontard G, Derat E, Lemiere G, Fensterbank L. Organometallics 2018; 37: 517

Supplementary Material

Supporting Information