Access to N-Alkylpyrazin-2-ones via C–O to C–N Rearrangement of Pyrazinyl Ethers

Vladimír Dacho; Dária Nitrayová; Michal Šoral; Andrea Machyňáková; Ján Moncoľ; Peter Szolcsányi

doi:10.1055/s-0039-1690222

SynOpen, Table of Contents

CC BY ND NC 4.0 · SynOpen 2019; 03(04): 108-113
DOI: 10.1055/s-0039-1690222

paper

Copyright with the author(s) (2019) The author(s)

Access to N-Alkylpyrazin-2-ones via C–O to C–N Rearrangement of Pyrazinyl Ethers

Authors

Vladimír Dacho

^aDepartment of Organic Chemistry, Slovak University of Technology in Bratislava, Radlinského 9, SK-81237 Bratislava, Slovakia Email: peter.szolcsanyi@stuba.sk
Dária Nitrayová

^aDepartment of Organic Chemistry, Slovak University of Technology in Bratislava, Radlinského 9, SK-81237 Bratislava, Slovakia Email: peter.szolcsanyi@stuba.sk
Michal Šoral

^bCentral Laboratories, Slovak University of Technology in Bratislava, Radlinského 9, SK-81237 Bratislava, Slovakia
Andrea Machyňáková

^cDepartment of Analytical Chemistry, Slovak University of Technology in Bratislava, Radlinského 9, SK-81237 Bratislava, Slovakia
Ján Moncoľ

^dDepartment of Inorganic Chemistry, Slovak University of Technology in Bratislava, Radlinského 9, SK-81237 Bratislava, Slovakia
Peter Szolcsányi ∗

^aDepartment of Organic Chemistry, Slovak University of Technology in Bratislava, Radlinského 9, SK-81237 Bratislava, Slovakia Email: peter.szolcsanyi@stuba.sk

Abstract

All articles of this category

Abstract

The reaction of tosylated 2-alkoxypyrazines with potassium halides led to the unexpected formation of N-alkylated pyrazinones. Such rare example of substitutive C–O → C–N rearrangement on pyrazines was then scrutinised by using various nucleophiles to afford the respective products in moderate to good yields. This method provides a direct access to N-alkylated-1H-pyrazin-2-ones. The formation of the rearranged products is conveniently and reliably determined by characteristic NMR shifts of their heteroaromatic protons.

Key words

pyrazinones - rearrangement - S_N reaction - NMR spectroscopy - X-ray crystal structure analysis

Full Text

References

References

1a Davis J, Benhaddou R, Granet R, Krausz P, Demonte M, Aubertin AM. Nucleosides Nucleotides 1998; 17: 875

Selected examples from the non-patent literature:

2a Nishiguchi GA, Rico A, Tanner H, Aversa RJ, Taft BR, Subramanian S, Setti L, Burger MT, Wan L, Tamez V, Smith A, Lou J, Barsanti AP, Appleton BA, Mamo M, Tandeske L, Dix I, Tellew JE, Huang S, Griner LA. M, Cooke VG, Van Abbema A, Merritt H, Ma S, Gampa K, Feng F, Yuan J, Wang Z, Haling JR, Vaziri S, Hekmat-Nejad M, Jansen JM, Polyakov V, Zang R, Sethuraman V, Amiri P, Singh M, Lees E, Shao W, Stuart DD, Dillon MP, Ramurthy S. J. Med. Chem. 2017; 60: 4869
2b Zhao L, Yang Y, Guo Y, Yang L, Zhang J, Zhou J, Zhang H. Bioorg. Med. Chem. 2017; 25: 2482
2c Carrer A, Brion J.-D, Messaoudi S, Alami M. Org. Lett. 2013; 15: 5606
2d Mandal D, Yamaguchi AD, Yamaguchi J, Itami K. J. Am. Chem. Soc. 2011; 133: 19660
2e Motohashi K, Inaba K, Fuse S, Doi T, Izumikawa M, Khan ST, Takahashi T, Shin-ya T. J. Nat. Prod. 2011; 74: 1630
2f Rao KV, Rock CP. J. Heterocycl. Chem. 1996; 33: 447
2g Nishio T, Tokunaga N, Kondo M, Omote Y. J. Chem. Soc., Perkin Trans. 1 1988; 2921
2h Goya P, Páez JA. Liebigs Ann. Chem. 1988; 121
2i Kočevar M, Stanovnik B, Tišler M. J. Heterocycl. Chem. 1982; 19: 1397

3 Mollet K, Goossens H, Piens N, Catak S, Waroquier M, Törnroos KW, Van Speybroeck V, D’hooghe M, De Kimpe N. Chem. Eur. J. 2013; 19: 3383

4a Schmarr H.-G, Sang W, Ganß S, Koschinski S, Meusinger R. J. Labelled Compd. Radiopharm. 2011; 54: 438
4b Candelon N, Shinkaruk S, Bennetau B, Bennetau-Pelissero C, Dumartin M.-L, Degueil M, Babin P. Tetrahedron 2010; 66: 2463
4c Yokoi T, Taguchi H, Nishiyama Y, Igarashi K, Kasuya F, Okada Y. J. Chem. Res., Miniprint 1997; 171

5 Bassindale AR, Parker DJ, Patel P, Taylor PG. Tetrahedron Lett. 2000; 41: 4933
6 Allinger NL, Zalkow V. J. Org. Chem. 1960; 25: 701
7 The Mitsunobu-type rearrangement: Nilsson B, Thor M, Cernerud M, Lundström H. PCT Int. Publ. WO 2004009586, 2004
8 The rearrangement of mesylate: Li H.-Y, McMillen WT, Wang Y. PCT Int. Publ. WO 2005092894, 2005
9 For an Au-catalysed version, see: Romero NA, Klepser BM, Anderson CE. Org. Lett. 2012; 14: 874

For an analogous C–O → C–N rearrangements on pyridines, see:

10a Lanni EL, Bosscher MA, Ooms BD, Shandro CA, Ellsworth BA, Anderson CE. J. Org. Chem. 2008; 73: 6425
10b Rodrigues A, Lee EE, Batey RA. Org. Lett. 2010; 12: 260
10c Tasker SZ, Brandsen BM, Ryu KA, Snapper GS, Staples RJ, DeKock RL, Anderson CE. Org. Lett. 2011; 13: 6224
10d Yeung CS, Hsieh TH. H, Dong VM. Chem. Sci. 2011; 2: 544
10e Tasker SZ, Bosscher MA, Shandro CA, Lanni EL, Ryu KA, Snapper GS, Utter JM, Ellsworth BA, Anderson CE. J. Org. Chem. 2012; 77: 8220
10f Pan S, Ryu N, Shibata T. Org. Lett. 2013; 15: 1902
10g Romero EO, Reidy CP, Bootsma AN, PreFontaine NM, Vryhof NW, Vierenga DC, Anderson CE. J. Org. Chem. 2016; 81: 9895
10h Cheng L.-J, Brown AP. N, Cordier CJ. Chem. Sci. 2017; 8: 4299
10i Xu G, Chen P, Liu P, Tang S, Zhang X, Sun J. Angew. Chem. Int. Ed. 2019; 58: 1890

11 Martin SF, Sahn JJ. Tetrahedron Lett. 2011; 52: 6855
12 Guthrie JP. Can. J. Chem. 1978; 56: 2342

13a Sheldrick GM. Acta Crystallogr., Sect. A: Found. Crystallogr. 2015; 71: 3
13b Bourhis LJ, Dolomanov OV, Gildea OV, Howard RJ, Puschmann JA. K. Acta Crystallogr., Sect. A: Found. Crystallogr. 2015; 71: 59
13c Dolomanov OV, Bourhis LJ, Gildea OV, Howard RJ, Puschmann JA. K. J. Appl. Crystallogr. 2009; 42: 339

Supplementary Material