8386
B.A. Shainyan et al. / Tetrahedron 66 (2010) 8383e8386
4.2. Synthesis
Forschungsgemeinschaft (Grants RFBR 10-03-00110 and RFBR-DFG
08-03-91954). We also thank Dr. Regine Herbst-Irmer (Institut für
€
€
4.2.1. Reaction of trifluoromethanesulfonamide with styrene. To the
mixture of trifluoromethanesulfonamide (2.3 g, 15.4 mmol), sty-
rene (3.18 g, 30.5 mmol), and NaI$2H2O (8.5 g, 46 mmol) in ace-
tonitrile (90 mL) t-BuOCl (5 g, 46 mmol) was added dropwise,
stirred in the dark at ꢀ10 ꢁC for 8 h, removed solvent in vacuum
without heating, the residue dissolved in chloroform, washed with
sodium thiosulfate solution, dried (MgSO4), and the solvent re-
moved in vacuum to yield 3 g of the crude product. About one third
part of it was dissolved in benzene and allowed to stay overnight.
The precipitate formed was filtered off and crystallized from chlo-
roform to give compound 4. The tarry residue of the crude product
(2 g) was chromatographed on a column with silica gel/60
0.063e0.200, using etherehexane (1:5, 1:2) and pure ether suc-
cessively as eluents. Elution with etherehexane (1:5) gave the
mixture of compounds 2 and 3, and final elution with ether gave
pure piperazine 4 (0.54 g, 14%). The mixture of 2 and 3 was further
purified on a column with fine-pore granulated silica gel of
0.015e0.040 mm granule size using etherehexane 1:1 as the eluent
to give the mixture of oily compound 3 and crystalline compound 2.
1-Phenyl-2-iodo-ethanol 3 (0.86 g, 21%) was separated from com-
pound 2 by dissolving in hexane with small amount of ether and
removal of solvent, the remaining crystals of trifluoro-N-[2-phenyl-
Anorganische Chemie, Universitat Gottingen) for her very useful
comments.
Supplementary data
Supplementary data include the details of X-ray structural
analysis, NMR, and IR spectra of the products, energy and
geometry of the diastereomers of 2,5-diphenyl-1,4-bis
(trifluoromethylsulfonyl)piperazine, 4. Supplementary data asso-
ciated with this article can be found in the online version, at
InChIKeys of the most important compounds described in this
article.
References and notes
1. Gontcharov, A. V.; Liu, H.; Sharpless, K. B. Org. Lett. 1999, 1, 783.
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3. Chanda, B. M.; Vyas, R.; Bedekar, A. V. J. Org. Chem. 2001, 66, 30.
4. Albone, D. P.; Aujla, P. S.; Taylor, P. C. J. Org. Chem. 1998, 63, 9569.
5. Ruppel, J. V.; Jones, J. E.; Huff, C. A.; Kamble, R. M.; Chen, Y.; Zhang, X. P. Org.
Lett. 2008, 1995.
2-(trifluoromethylsulfonyl)aminoethyl] methanesulfonamide
(1.6 g, 52%) were filtered off.
2
6. Han, H.; Park, S. B.; Kim, S. K.; Chang, S. J. Org. Chem. 2008, 73, 2862.
7. Nadir, U. K.; Singh, A. Synth. Commun. 2004, 34, 1337.
4.2.2. Trifluoro-N-[2-phenyl-2-(trifluoromethylsulfonyl)aminoethyl]-
methanesulfonamide, 2. Mp 94e96 ꢁC; nmax (KBr) 3331 (NH), 3307
8. Minakata, S.; Morino, Y.; Oderaotoshi, Y.; Komatsu, M. Chem. Commun. 2006,
3337.
9. Sweeney, J. B. Chem. Soc. Rev. 2002, 31, 247.
(NH), 1461, 1442, 1373, 1231, 1201, 1141, 1062, 1050, 982, 891 cmꢀ1
;
10. Singh, G. S.; D’hooghe, M.; De Kimpe, N. Chem. Rev. 2007, 107, 2080.
dH (CD3CN) 7.42 (5H, m, Ph), 7.2 (2H, br s, NH), 4.76 (1H, d, J 6.9 Hz,
PhCH), 3.60 (2H, d, J 7.1 Hz, PhCHCH2); dH (C6D6) 7.10 (5H, m, Ph), 5.5
(2H, br s, NH), 4.61 (1H, dd, J 8.4, 4.5 Hz, PhCH), 3.19 (1H, dd, J 14.2,
8.4 Hz, PhCHCHB), 3.09 (1H, dd, J 14.2, 4.5 Hz, PhCHCHA); dC (CD3CN)
138.1 (Ci), 130.1 (Co), 129.8 (Cp), 127.8 (Cm), 120.8 (q, J 320.7 Hz, 2-
11. Minakata, S. Acc. Chem. Res. 2009, 42, 1172.
12. Nelson, S. G.; Mills, P. M. Org. Synth. 2005, 82, 170.
13. Zhu, S.-Z. J. Chem. Soc., Perkin Trans. 1 1994, 2077.
14. (a) Shainyan, B. A.; Meshcheryakov, V. I. Russ. J. Org. Chem. 2001, 37, 1797; (b)
Mescheryakov, V. I.; Albanov, A. I.; Shainyan, B. A. Russ. J. Org. Chem. 2005,
41, 1381; Mescheryakov, V. I.; Shainyan, B. A.; Zavodnik, V. E.; Bel’skii, V. K.
Russ. J. Org. Chem. 2006, 42, 1254; Mescheryakov, V. I.; Danilevich, Y. S.;
Moskalik, M. Y.; Stetsjura, N. Y.; Zavodnik, V. E.; Bel’skii, V. K.; Shainyan, B. A.
Russ. J. Org. Chem. 2007, 43, 793; Mescheryakov, V. I.; Moskalik, M. Y.; Kel-
ling, A.; Schilde, U.; Ushakov, I. A.; Shainyan, B. A. Russ. J. Org. Chem. 2008,
44, 311; Shainyan, B. A.; Meshcheryakov, V. I. Mini-Rev. Org. Chem. 2009, 6,
66.
CF3), 120.6 (q, J 320.4 Hz, 1-CF3), 60.8 (CH), 49.8 (CH2). 19F NMR, dF
,
ppm: ꢀ78.80 (1-CF3), ꢀ78.58 (2-CF3). HRMS (ESI): [MþNa]þ, found
422.9865. C10H10F6N2O4S2Na requires 422.9884.
4.2.3. 1-Phenyl-2-iodo-ethanol, 3. Oil with crystals; lit. mp 34 ꢁC;20
dH (CD3CN) 7.40 m (5H, m, Ph), 4.78 (1H, ddd, J 7.4, 4.5, 3.9 Hz,
PhCH), 3.76 (1H, d, J 3.9 Hz, OH), 3.52 (1H, dd, J 10.1, 4.5 Hz,
PhCHCHB), 3.42 (1H, dd, J 10.1, 7.4 Hz, PhCHCHA); dC (CD3CN) 143.6
(Ci), 129.2 (Cm), 128.6 (Cp), 126.7 (Co), 73.8 (d, J 146.0 Hz, CH), 15.6
(t, JCH 151.1 Hz, CH2I).
15. Lake, F.; Moberg, C. Eur. J. Org. Chem. 2002, 3179.
16. Pandey, M. K.; Bisai, A.; Singh, V. K. Tetrahedron Lett. 2000, 45, 9661.
17. Kumar, M.; Gandhi, S.; Kalra, S. S.; Singh, V. K. Synth. Commun. 2008, 38, 1527.
18. Wu, J.; Sun, X.; Xia, H.-G. Eur. J. Org. Chem. 2005, 4769.
19. Golumbic, C.; Cottle, D. L. J. Am. Chem. Soc. 1939, 61, 996.
20. Villegas, R. A. S.; Santo, J. L. E., Jr.; de Mattos, M. C. S.; de Aguiar, M. R. M. P.;
Guarino, A. W. S. J. Braz. Chem. Soc. 2005, 16, 565.
21. Knipe, A. C.; Khandelwal, Y.; McAuley, I. E.; Brown, N. M. D. Magn. Reson.
Chem. 1985, 23, 177; Forni, A.; Moretti, I.; Mucci, A.; Prati, F.; Schenetti, L.
Chem. Heterocycl. Comp. 1995, 31, 1071; Joly, G. J.; Peeters, K.; Mao, H.;
Brossette, T.; Hoornaert, G. J.; Compernolle, F. Tetrahedron Lett. 2000, 41,
2223.
4.2.4. 2,5-Diphenyl-1,4-bis(trifluoromethylsulfonyl)piperazine,
4. Mp 130.5 ꢁC; nmax (KBr) 3070, 3038, 2929, 1628, 1499, 1457, 1399,
1229, 1201, 1140, 1122, 1056, 1028, 954, 909, 875, 698 cmꢀ1
; dH
22. Crystal data for 4: 3(C18H16F6N2O4S2)$C2H5OH, Mr¼1553.56 g molꢀ1, crystal
dimensions 0.25ꢂ0.25ꢂ0.15 mm, monoclinic, space group P21/n, a¼18.3378
(CD3CN) 7.46m (5H, Ph), 5.32 (1H, dd, J 11.2, 6.8 Hz, PhCH), 4.40 (1H,
dd, J 15.5, 6.8 Hz, PhCHCHB), 4.01 (1H, dd, J 15.5, 11.2 Hz, PhCHCHA);
dC (CD3CN) 137.7 (Ci), 130.2 (Cp), 130.0 (Cm), 127.5 (Co), 120.5 q (CF3,
(13), b¼11.6748(5), c¼32.096(2) Å, V¼6870.4(7) Å3, Z¼4, rcalcd¼1.485 g cmꢀ1
;
m
(Mo K
a
)¼0.31 mmꢀ1
(
l
¼0.71073 Å), T¼210 K; 2Qmax¼49.16ꢁ, 40,714 re-
flections measured, 11,520 unique (Rint¼0.0960), R¼0.0581, wR¼0.1232 (I>2
s
1
1 A
JCF 321.1 Hz), 61.7 (CH, JCH 148.4 Hz), 48.6 (CH2,
J
146.7,
CH
(i)) For details of the data collection and the structure solution and refinement
see Supplementary data. CCDC-766328 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free of charge from the
1 B
J
CH
148.8 Hz). 19F NMR, dF, ppm: ꢀ77.34. HRMS (ESI): [MþNa]þ,
found 525.0347. C18H16F6N2O4S2Na requires 525.0353.
23. Heine, H. W.; Canyon, W. G.; Johnson, E. M. J. Am. Chem. Soc. 1961, 83,
2570.
Acknowledgements
24. Okada, I.; Itoh, N.; Sudo, R. Bull. Chem. Soc. 1969, 42, 547.
25. Porter, Q. N. Mass Spectrometry of Heterocyclic Compounds; John Wiley:
New York, NY, 1985.
We gratefully acknowledge supporting of this work by the
Russian Foundation for Basic Research and Deutsche