Electron-Withdrawing Diamide Receptors/Organocatalysts
392 [M + H]+. HRMS: m/z for C17H10NO3F6 (M–) calcd. 390.0565; Supporting Information (see footnote on the first page of this arti-
found 390.0562.
cle): Full experimental procedures, characterisation data, NMR
stack plots and rate plots.
To ester 8 (1.67 g, 4.26 mmol) dissolved in hot methanol (40 mL)
was added 1 m NaOH, (20 mL, 20 mmol) and the mixture was re-
fluxed with stirring for one hour. Distilled water (100 mL) was
added to the mixture which was then acidified to pH 3 with concen-
trated aqueous HCl. The mixture was cooled and filtered to give 9
Acknowledgments
We would like to thank the Irish Research Council for Science,
Engineering and Technology and Waterford Institute of Technol-
ogy for funding provided, University College Cork for HRMS
work, Professor Michael Hynes at National University of Ireland,
Galway and Dr Helen Hughes at Waterford Institute of Technology
for many helpful discussions.
(1.24 g, 77%) as a white solid; m.p. 194–196 °C. IR (KBr): ν
=
˜
max
3292, 3092, 2662, 2551, 1690, 1651, 1562, 1470, 1441, 1381, 1305,
1279, 1175, 1146, 943, 893, 728 and 683. 1H NMR (400 MHz; [D6]-
DMSO, 22 °C): δ = 13.3 (br. s, 1 H, OH), 11.02 (s, 1 H, N–H), 8.57
(s, 1 H, 2-H), 8.51 (s, 2 H, 2Ј-H), 8.21 (d, JH,H = 7.6 Hz, 1 H, 6-
H), 8.15, (d, JH,H = 7.6 Hz, 1 H, 4-H), 7.80 (s, 1 H, 4Ј-H), 7.67 (t,
JH,H = 7.6 Hz, 1 H, 5-H) ppm. 13C NMR (100 MHz; [D6]DMSO,
22 °C): δ = 166.7, 165.4, 134.2, 132.8, 132.2, 130.8, 129.1, 128.5,
124.6, 121.9, 120, 116.6 ppm. LRMS (ES+): m/z = 378 [M + H]+.
HRMS: m/z for C16H8NO3F6 (M–) calcd. 376.0484; found
376.0423.
[1] G. W. Bates, P. A. Gale, in: Recognition of Anions, vol. 129,
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[2] For an example of an indole-based receptor, see: F. M. Pfeffer,
K. F. Lim, K. J. Sedgwick, Org. Biomol. Chem. 2007, 5, 1795–
1799; for an example of a pyrrole based receptor, see: T. Zielin-
ski, J. Jurczak, Tetrahedron 2005, 61, 4081–4089; for an exam-
ple of a sulfonamide-based receptor, see: M. T. Huggins, T.
Butler, P. Barber, J. Hunt, Chem. Commun. 2009, 5254–5256;
for an example of a urea-based receptor, see: C. Lin, V. Simov,
D. G. Drueckhammer, J. Org. Chem. 2007, 72, 1742–1746.
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129, 1886–1887.
Aqueous ammonia (2 mL), triethylamine (3.64 mmol, 0.5 mL) were
added to DMF (20 mL), the reaction mixture cooled to 0 °C and
to this was added dropwise 3,5-bis(trifluoromethyl)benzenesulfonyl
chloride (0.5 g, 1.6 mmol). The reaction mixture was stirred at
room temperature for 16 h and to this was added 300 mL distilled
water. The basic reaction mixture was acidified to pH 2 by addition
of concentrated HCl causing the product to precipitate out of solu-
tion. The off-white precipitate 10 (0.46 g, 98%) was collected by
[5] P. S. Bhadury, B. A. Song, S. Yang, D. Y. Hu, W. Xue, Curr.
Org. Synth. 2009, 6, 380–399.
filtration; m.p. 184.5–185 °C. IR (KBr): ν
= 3356, 3262, 3097,
˜
max
1
3067, 1862, 1833, 1626, 1531, 1457, 1324, 1197 and 907. H NMR
(400 MHz; [D6]DMSO, 22 °C): δ = 8.46 (s, 1 H, 4-H), 8.40 (s, 2 H,
2-H), 7.79 (s, 1 H, NH2) ppm. 13C NMR (100 MHz; [D6]DMSO,
22 °C): δ = 147, 131, 127, 124.6, 121.9 ppm. LRMS (ES+): m/z =
294 [M + H]+. HRMS: m/z for C8H4NO2F6S (M–) calcd. 291.9867;
found 291.9864.
[6] Y. Sohtome, N. Takemura, R. Takagi, Y. Hashimoto, K. Naga-
sawa, Tetrahedron 2008, 64, 9423–9429; S. J. Connon, Chem.
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Fan, C. Vicent, A. D. Hamilton, New J. Chem. 1997, 21, 81–
85; S. E. Reisman, A. G. Doyle, E. N. Jacobsen, J. Am. Chem.
Soc. 2008, 130, 7198–7199; I. T. Raheem, P. S. Thiara, E. A.
Peterson, E. N. Jacobsen, J. Am. Chem. Soc. 2007, 129, 13404;
R. H. Crabtree, K. Kavallieratos, Chem. Commun. 1999, 2109–
2110.
Acid 9 (370.5 mg, 0.98 mmol) was dissolved in a 50:50 mixture of
dichloroethane:tert-butyl alcohol (20 mL) and to this stirred sus-
pension was added DMAP (360 mg, 2.95 mmol), EDCI (472 mg,
2.46 mmol) and 3,5-bis(trifluoromethyl)benzenesulfonamide (10)
(200 mg, 0.68 mmol). The reaction mixture was stirred for 72 h at
room temperature and after this time Amberlyst 15 anion exchange
resin (2 g) was added and the mixture was diluted with ethyl acetate
(10 mL). This mixture was stirred for a further 2 h and sub-
sequently passed through a plug of silica gel and washed with ethyl
acetate. The filtrate was collected and solvent removed in vacuo.
The crude product was purified by flash chromatography (98%
dichloromethane/2% methanol) to give product 7 (187 mg, 43%)
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Bertao, R. H. Crabtree, J. Org. Chem. 1999, 64, 1675–1683.
[9] Over the course of this work, the synthesis of 3 and 5 were
reported along with application of 5 in a Diels–Alder reaction.
To the best of our knowledge, a comprehensive anion binding
study and application of these compounds in other reactions
has not been conducted.[10]
[10] F. M. Muñiz, V. A. Montero, Á. L. Fuentes de Arriba, L.
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as an off white solid, m.p. 241.5–242.3 °C. IR (KBr): ν
= 3450,
˜
max
3318, 3093, 2927, 1667, 1608, 1553, 1471, 1380, 1353, 1179, 888,
1
844 and 682. H NMR (400 MHz, CD3CN, 22 °C): δ = 9.37 (s, 1
H, Amide N–H), 8.61 (s, 1 H, 2-H), 8.52 (s, 2 H, 2ЈЈ-H), 8.33 (s, 2
H, 2Ј-H), 8.13 (d, JH,H = 7.6 Hz, 1 H, 6-H), 8.09 (s, 1 H, 4ЈЈ-H),
7.96 (d, JH,H = 7.6 Hz, 1 H, 4-H), 7.69 (s, 1 H, 4Ј-H), 7.39 (t, JH,H
=
7.6 Hz, 1 H, 5-H) ppm. 13C NMR (100 MHz; [D6]DMSO, 22 °C): δ
= 169, 166, 148, 141, 138, 133, 132, 130, 128, 127.9, 127.6, 124.7,
124.4, 123.9, 122, 121.7, 120, 116 ppm. LRMS (ES–): m/z = 651
[M – H]–. HRMS: m/z for C24H11N2O4F12S (M–) calcd. 651.0248;
found 651.0242.
CCDC-796511 contains the supplementary crystallographic data
for 5. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
[15] M. H. Abraham, Chem. Soc. Rev. 1993, 22, 73–83.
[16] H.-J. Lee, Y.-S. Choi, K.-B. Lee, J. Park, C.-J. Yoon, J. Phys.
Chem. A 2002, 106, 7010–7017.
Eur. J. Org. Chem. 2011, 1125–1132
© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
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