Synthesis of Novel Molecular
Clips via Click Chemistry Based on Diethoxy carbonyl Glycoluril

Meng Gao; Liping Cao; Zihua Wang; Jingjing Sun; Nengfang She; Anxin Wu

doi:10.1055/s-0028-1087670

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Synlett 2009(2): 315-319
DOI: 10.1055/s-0028-1087670

LETTER

Synthesis of Novel Molecular Clips via Click Chemistry Based on Diethoxy carbonyl Glycoluril

Meng Gao, Liping Cao, Zihua Wang, Jingjing Sun, Nengfang She, Anxin Wu*
Key Laboratory of Pesticide & Chemical Biology, Ministry of Education, Central China Normal University, Wuhan 430079, P. R. of China
e-Mail: chwuax@mail.ccnu.edu.cn;

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Publication History

Received 8 September 2008
Publication Date:
15 January 2009 (online)

Abstract
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Abstract

A novel class of molecular clips based on diethoxycarbonyl glycoluril was synthesized via click chemistry. Seven different arylacetylenes were used in this research, and all reaction products gave satisfying ^¹H NMR, ^¹³C NMR, HRMS, and IR spectra. The structure and conformation of 7a were further confirmed by single-crystal X-ray diffraction. A primary study on the metal-ion binding ability of 7f showed that its fluorescence was obviously quenched by Fe^³+, Ag⁺, and Cu^²+ among metal ions examined.

Key words

clip receptor - diethoxycarbonyl glycoluril - molecular recognition - 1,2,3-triazole - fluorescence

Supporting Information

References and Notes

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Compound 5: IR (KBr): 2984, 1721, 1598, 1415, 1358, 1176, 907, 817, 663, 554 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 7.78 (d, J = 8.4 Hz, 4 H), 7.35 (d, J = 8.4 Hz, 4 H), 4.73 (d, J = 14.4 Hz, 4 H), 4.30-4.25 (m, 8 H), 4.04 (t, J = 5.2 Hz, 4 H), 2.90 (t, J = 5.2 Hz, 4 H), 2.48 (s, 6 H), 1.30 (t, J = 7.2 Hz, 6 H). ^¹³C NMR (150 MHz, CDCl₃): δ = 164.8, 158.3, 144.8, 132.5, 129.7, 127.7, 75.8, 67.2, 63.3, 59.7, 49.7, 21.4, 13.6. ESI-MS: m/z = 765.0 [M + H]⁺.

21

Compound 6: IR (KBr): 2989, 2100, 1767, 1709, 1407, 1276, 899, 725 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 4.88 (d, J = 14.0 Hz, 4 H), 4.36 (d, J = 14.0 Hz, 4 H), 4.30 (q, J = 7.2 Hz, 4 H), 3.36 (t, J = 5.6 Hz, 4 H), 2.90 (t, J = 5.6 Hz, 6 H), 1.32 (t, J = 7.2 Hz, 6 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 165.0, 158.4, 76.0, 63.4, 59.9, 50.4, 48.6, 13.8. ESI-MS: m/z = 506.2 [M]⁺.

26

General Procedure for the Synthesis of Compound 7
The azide 6 (0.20 mmol) and arylacetylene (0.40 mmol) were suspended in 1:1 mixture of H₂O and t-BuOH (10 mL). Ascorbate acid (0.020 mmol, 20 µL of freshly prepared 1.0 M solution in H₂O, 10 mol%) was added, followed by copper(II) sulfate pentahydrate (0.010 mmol, 100 µL of 0.10 M solution in H₂O, 5.0 mol%). The heterogeneous mixture was stirred vigorously for 24 h under Ar protection. After total consumption of the starting material (determination by TLC), the solvent was removed in vacuo, and the residue was isolated by column chromatography on SiO₂ to get the pure product 7.
Compound 7a: IR (KBr): 3244, 2985, 1705, 1444, 1282, 1047, 767, 697 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 7.86 (d, J = 7.6 Hz, 4 H), 7.60 (s, 2 H), 7.45 (t, J = 7.6 Hz, 4 H), 7.35 (t, J = 7.6 Hz, 2 H), 4.82 (d, J = 13.6 Hz, 4 H), 4.36 (t, J = 6.0 Hz, 4 H), 4.28 (q, J = 7.2 Hz, 4 H), 4.19 (d, J = 13.6 Hz, 4 H), 2.93 (t, J = 6.0 Hz, 4 H), 1.30 (t, J = 7.2 Hz, 6 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 164.9, 158.6, 147.3, 130.6, 128.9, 128.1, 125.6, 120.3, 76.0, 63.5, 60.0, 50.1, 47.0, 13.8. ESI-HRMS: m/z [M + Na]⁺ calcd for C₃₄H₃₈N₁₂NaO₆: 733.2929; found: 733.2898.
Compound 7b: IR (KBr): 3423, 3137, 2988, 1766, 1730, 1707, 1612, 1411, 1286, 1234, 1045, 907, 718 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 8.68 (d, J = 5.6 Hz, 4 H), 7.88 (s, 2 H), 7.77 (d, J = 5.6 Hz, 4 H), 4.81 (d, J = 13.6 Hz, 4 H), 4.45 (t, J = 5.2 Hz, 4 H), 4.31-4.22 (m, 8 H), 3.03 (t, J = 5.2 Hz, 4 H), 1.31 (t, J = 7.2 Hz, 6 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 164.7, 158.5, 150.3, 144.9, 137.9, 122.0, 119.8, 75.9, 63.6, 59.9, 50.1, 47.6, 13.8. ESI-HRMS: m/z [M+Na]⁺ calcd for C₃₂H₃₆N₁₄NaO₆: 735.2834; found: 735.2814.
Compound 7c: IR (KBr): 3447, 3134, 2939, 2840, 1760, 1718, 1459, 1299, 1248, 1231, 1027, 825, 717 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 7.78 (d, J = 8.4 Hz, 4 H), 7.50 (s, 2 H), 6.97 (d, J = 8.4 Hz, 4 H), 4.82 (d, J = 13.2 Hz, 4 H), 4.33-4.25 (m, 8 H), 4.18 (d, J = 13.2 Hz, 4 H), 3.80 (s, 6 H), 2.88 (t, J = 6.0 Hz, 4 H), 1.30 (t, J = 7.2 Hz, 6 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 164.9, 159.5, 158.5, 147.2, 126.9, 123.3, 119.5, 114.2, 76.0, 63.5, 60.0, 55.2, 50.1, 46.8, 13.8. ESI-HRMS: m/z [M + Na]⁺ calcd for C₃₆H₄₂N₁₂NaO₈: 793.3141; found: 793.3100.
Compound 7d: IR (KBr): 3448, 3367, 2982, 2849, 1720, 1621, 1502, 1416, 1291, 1233, 1029, 906, 837, 715 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 7.61 (d, J = 8.0 Hz, 4 H), 7.48 (s, 2 H), 6.68 (d, J = 8.0 Hz, 4 H), 4.79 (d, J = 13.6 Hz, 4 H), 4.28-4.24 (m, 8 H), 4.12 (d, J = 13.6 Hz, 4 H), 3.90 (br s, 4 H), 2.87 (t, J = 6.0 Hz, 4 H), 1.27 (t, J = 7.2 Hz, 6 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 164.9, 158.5, 147.6, 146.7, 126.7, 120.6, 119.1, 115.1, 76.0, 63.5, 59.9, 50.0, 46.7, 13.8. ESI-HRMS: m/z [M + Na]⁺ calcd for C₃₄H₄₀N₁₄NaO₆: 763.3147; found: 763.3120.
Compound 7e: IR (KBr): 3362, 3150, 2984, 2844, 1726, 1678, 1617, 1414, 1235, 1030, 982, 910, 858, 776, 713 cm^-¹. ^¹H NMR (400 MHz, DMSO-d ₆): δ = 8.50 (s, 2 H), 8.02 (s, 2 H), 7.98 (d, J = 8.0 Hz, 4 H), 7.91 (d, J = 8.0 Hz, 4 H), 7.42 (s, 2 H), 4.78 (d, J = 13.6 Hz, 4 H), 4.50 (t, J = 6.0 Hz, 4 H), 4.29-4.21 (m, 8 H), 3.01 (t, J = 6.0 Hz, 4 H), 1.21 (t, J = 7.2 Hz, 6 H). ^¹³C NMR (100 MHz, DMSO-d ₆): δ = 167.5, 164.9, 158.3, 145.4, 133.4, 133.3, 128.3, 124.8, 122.5, 75.8, 63.5, 59.3, 49.6, 46.9, 13.7. ESI-HRMS: m/z [M + Na]⁺ calcd for C₃₆H₄₀N₁₄NaO₈: 819.3046; found: 819.2999.
Compound 7f: IR (KBr): 3423, 3137, 2988, 1766, 1730, 1707, 1612, 1411, 1286, 1234, 1045, 907, 718 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 8.43 (d, J = 8.0 Hz, 2 H), 7.82 (d, J = 8.0 Hz, 4 H), 7.70 (d, J = 8.0 Hz, 2 H), 7.55-7.47 (m, 8 H), 4.82 (d, J = 13.6 Hz, 4 H), 4.34 (t, J = 6.0 Hz, 4 H), 4.27 (q, J = 7.2 Hz, 4 H), 4.20 (d, J = 13.6 Hz, 4 H), 2.95 (t, J = 6.0 Hz, 4 H), 1.28 (t, J = 7.2 Hz, 6 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 164.8, 158.5, 146.5, 133.7, 130.7, 128.8, 128.3, 127.8, 127.1, 126.7, 126.0, 125.4, 125.3, 122.9, 75.9, 63.5, 60.0, 50.2, 47.1, 13.8. ESI-HRMS: m/z [M + Na]⁺ calcd for C₄₂H₄₂N₁₂NaO₆: 833.3242; found: 833.3220.
Compound 7g: IR (KBr): 3448, 3122, 2982, 1719, 1414, 1232, 1035, 906, 821, 712, 505, 488 cm^-¹. ^¹H NMR (400 MHz, CDCl₃): δ = 7.47 (s, 2 H), 4.81-4.78 (m, 8 H), 4.34-4.30 (m, 8 H), 4.27 (q, J = 7.2 Hz, 4 H), 4.20 (d, J = 13.2 Hz, 4 H), 4.10 (s, 10 H), 2.94 (t, J = 5.6 Hz, 4 H), 1.29 (t, J = 7.2 Hz, 6 H). ^¹³C NMR (100 MHz, CDCl₃): δ = 164.9, 158.5, 146.4, 119.5, 76.0, 75.5, 69.6, 68.6, 66.5, 63.5, 60.0, 50.3, 47.1, 13.8. ESI-HRMS: m/z [M + Na]⁺ calcd for C₄₂H₄₆Fe₂N₁₂NaO₆: 949.2273; found:949.2215.

27

Crystal Data for Compound 7a
C₃₄H₃₈N₁₂O₆, MW = 710.78, triclinic, a = 10.0153 (5), b = 12.0495 (6), c = 16.3995 (8) Å, α = 102.658 (0)˚, β = 103.272 (0)˚, γ = 108.398 (0)˚, V = 1734.28 (15) Å^³, T = 294 (2) K, space group Z = 4, m(MoKα) = 0.094 mm^-¹, 15230 reflections measured, 6724 unique (Rint = 0.0981) which were used in all calculations. The final wR ₂ (F ₂) was 0.1531. CCDC 699457 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

Supplementary Material

Supporting Information