Synlett 2006(1): 0049-0052  
DOI: 10.1055/s-2005-922761
LETTER
© Georg Thieme Verlag Stuttgart · New York

Synthesis of Novel Molecular Clips Based on Diethoxycarbonyl Glycoluril

Guodong Yina, Zhiguo Wanga, Yunfeng Chena, Anxin Wu*a, Yuanjiang Pan*b
a Key Laboratory of Pesticide and Chemical Biology, Ministry of Education, Central China Normal University, Wuhan 430079, P. R. of China
e-Mail: chwuax@mail.ccnu.edu.cn;
b Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. of China
e-Mail: panyuanjiang@zju.edu.cn;
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Publikationsverlauf

Received 26 September 2005
Publikationsdatum:
16. Dezember 2005 (online)

Abstract

A novel class of molecular clips was synthesized, which are soluble in most non-polar organic solvents. Aromatic amines and diethoxycarbonyl glycoluril were used for the first time in this type of reaction. All reaction products gave satisfying 1H NMR, 13C NMR, MS, and IR spectra. In addition, the structure and conformation of 4d were confirmed by single crystal X-ray diffraction.

    References and Notes

  • 1 Diederich F. Cyclophanes   The Royal Society of Chemistry; Cambridge: 1991. 
  • 2 Lehn JM. Supramolecular Chemistry, Concepts and Perspectives   VCH; Weinheim: 1995. 
  • 3 Purse BW. Rebek J. Proc. Natl. Acad. Sci. U.S.A.  2005,  102:  10777 
  • 4a Rebek J. Science  1987,  235:  1478 
  • 4b Shimizu KD. Dewey TM. Rebek J. J. Am. Chem. Soc.  1994,  116:  5145 
  • 4c Warrener RN. Margetic D. Amarasekara AS. Butler DN. Mahadevan IB. Russell RA. Org. Lett.  1999,  1:  199 
  • 5 Adrian JC. Wilcox CS. J. Am. Chem. Soc.  1989,  111:  8055 
  • 6 Sanderson PEJ. Kilburn JD. Still WC. J. Am. Chem. Soc.  1989,  111:  8314 
  • 7 Chen CW. Whitlock HW. J. Am. Chem. Soc.  1978,  100:  4921 
  • 8 Zimmerman SC. VanZyl CM. J. Am. Chem. Soc.  1987,  109:  7894 
  • 9 Zimmerman SC. Wu W. J. Am. Chem. Soc.  1989,  111:  8054 
  • 10 Klärner FG. Kahlert B. Acc. Chem. Res.  2003,  36:  919 
  • 11 Harmata M. Acc. Chem. Res.  2004,  37:  862 
  • 12a Klärner FG. Lobert M. Naatz U. Bandmann H. Boese R. Chem.-Eur. J.  2003,  9:  5036 
  • 12b Wu A. Chakraborty A. Fettinger JC. Flowers RA. Isaacs L. Angew. Chem. Int. Ed.  2002,  41:  4028 
  • 13 Dixon RP. Geib SJ. Hamilton AD. J. Am. Chem. Soc.  1992,  114:  365 
  • 14a Paliwal S. Geib S. Wilcox CS. J. Am. Chem. Soc.  1994,  116:  4497 
  • 14b Lagona J. Fettinger JC. Isaacs L. Org. Lett.  2003,  5:  3745 
  • 15a Sijbesma RP. Nolte RJM. J. Org. Chem.  1991,  56:  3122 
  • 15b Sijbesma RP. Wijmenga SS. Nolte RJM. J. Am. Chem. Soc.  1992,  114:  9807 
  • 15c Sijbesma RP. Kentgens APM. Lutz ETG. van der Maas JH. Nolte RJM. J. Am. Chem. Soc.  1993,  115:  8999 
  • 15d Reek JNH. Priem AH. Engelkamp H. Rowan AE. Elemans JAAW. Nolte RJM. J. Am. Chem. Soc.  1997,  119:  9956 
  • 15e Rowan AE. Elemans JAAW. Nolte RJM. Acc. Chem. Res.  1999,  32:  995 
  • 15f Jansen RJ. de Gelder R. Rowan AE. Scheeren HW. Nolte RJM. J. Org. Chem.  2001,  66:  2643 
  • 16 Savostianoff DFr. inventors; Patent Appl.  2 291 203.  ; Chem. Abstr. 1977, 86, 121377n
  • 17 Mock WL. Manimaran T. Freeman WA. Kuksuk RM. Maggio JE. Williams DH. J. Org. Chem.  1985,  50:  60 
  • 18 Liu S. Wu X. Zhang S. Yao J. Liang F. Wu C. New J. Chem.  2004,  28:  562 
  • 19 Burnett CA. Logona J. Wu A. Shaw JA. Coady D. Fettinger JC. Day AI. Isaacs L. Tetrahedron  2003,  59:  1961 
  • 20 Smeets JWH. Sijbesma RP. Niele FGM. Spek AL. Smeets WJJ. Nolte RJM. J. Am. Chem. Soc.  1987,  109:  928 
  • 21 Nunen JLM. Nolte RJM. J. Chem. Soc., Perkin Trans. 2  1997,  1473 
  • 23 Crystal data for compound 4d: C28H32N6O8, M = 580.60, triclinic, a = 7.5266 (18), b = 13.438 (3), c = 14.167 (3) Å, a = 87.547 (4)°, β = 83.627 (4)°, γ = 81.942 (4)°, U = 1409.4 (6) Å3, T = 292 (2) K, space group P-1, Z = 2, µ (Mo-Kα) = 0.102 mm-1, 7110 reflections measured, 4870 unique (R int = 0.0216) which were used in all calculations. The final wR 2 (F 2) was 0.1816 (all data). CCDC-281947 contains the supplementary crystallographic data for this paper. These data can be obtained free of charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(1223)336033; email: deposit@ccdc.cam.ac.uk]
22

Compound 4a: IR (KBr): 3457 (m), 2850 (m), 1762 (s), 1731 (s), 1464 (m), 1419 (m), 1389 (m), 1251 (s), 1173 (m), 1054 (m), 950 (m), 761 (m), 699 (m) cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.12 (t, 4 H), 6.94-6.88 (m, 6 H), 5.49 (d, 4 H, J = 13.2 Hz), 4.56 (d, 4 H, J = 13.2 Hz), 4.33 (q, 4 H, J = 6.8 Hz), 1.35 (t, 6 H, J = 6.8 Hz). 13C NMR (100 MHz, CDCl3): δ = 165.13, 157.32, 145.86, 129.24, 121.71, 117.73, 76.13, 63.33, 58.31, 13.84. MS: m/z (%) = 521 (100) [M+], 416 (68), 387 (95), 343 (61), 240 (31), 105 (93).
Compound 4b: IR (KBr): 3456 (m), 2861 (m), 1763 (s), 1731 (s), 1522 (m), 1465 (m), 1418 (m), 1392 (m), 1247 (s), 1176 (m), 1052 (m), 944 (m), 809 (m) cm-1. 1H NMR (400 MHz, CDCl3): δ = 6.92 (d, 4 H), 6.83 (d, 4 H), 5.43 (d, 4 H, J = 13.2 Hz), 4.53 (d, 4 H, J = 13.2 Hz), 4.32 (q, 4 H, J = 6.8 Hz), 2.24 (s, 6 H), 1.34 (t, 6 H, J = 6.8 Hz). 13C NMR (100 MHz, CDCl3): δ = 165.18, 157.30, 143.58, 130.92, 129.73, 117.92, 76.09, 63.26, 58.51, 20.44, 13.81. MS: m/z (%) = 549 (100) [M+], 400(91), 356 (41), 118 (88).
Compound 4c: IR (KBr): 3453 (m), 2919 (m), 2847 (m), 1765 (s), 1727 (s), 1465 (m), 1412 (m), 1384 (m), 1248 (s), 1158 (m), 1057 (m), 936 (m), 782 (m), 701 (m) cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.04 (2 H), 6.80-6.72 (m, 6 H), 5.46 (d, 4 H, J = 13.2 Hz), 4.51 (d, 4 H, J = 13.2 Hz), 4.33 (q, 4 H, J = 7.2 Hz), 2.20 (s, 6 H), 1.35 (t, 6 H, J = 7.2 Hz). 13C NMR (100 MHz, CDCl3): δ = 165.22, 157.44, 145.98, 139.00, 128.98, 122.84, 118.81, 115.03, 76.09, 63.34, 58.68, 21.44, 13.87. MS: m/z (%) = 549 (100) [M+], 400(97), 356 (49), 118 (60).
Compound 4d: IR (KBr): 3451 (s), 2987 (m), 2939 (m), 1768 (s), 1729 (s), 1515 (s), 1463 (m), 1416 (m), 1284 (m), 1242 (s), 1179 (m), 1032 (m), 824 (m) cm-1. 1H NMR (400 MHz, CDCl3): δ = 6.93 (d, 4 H, J = 8.8 Hz), 6.71 (d, 4 H, J = 8.8 Hz), 5.34 (d, 4 H, J = 12.8 Hz), 4.53 (d, 4 H, J = 12.8 Hz), 4.33 (q, 4 H, J = 7.2 Hz), 3.73 (s, 6 H), 1.34 (t, 6 H, J = 7.2 Hz). 13C NMR (100 MHz, CDCl3): δ = 165.21, 157.48, 154.91, 139.73, 120.12, 114.40, 76.05, 63.27, 59.32, 55.20, 13.83. MS: m/z (%) = 581 (100)[M+], 416 (41), 372 (26), 191 (27), 176 (30), 134 (99), 120 (71).
Compound 4e: IR (KBr): 3457 (m), 2962 (m), 1753 (s), 1737 (s), 1261 (s), 1093 (s), 1050 (s), 802 (s) cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.05 (d, 4 H, J = 8.8 Hz), 6.90 (d, 4 H, J = 8.8 Hz), 5.41 (d, 4 H, J = 12.8 Hz), 4.49 (d, 4 H, J = 12.8 Hz), 4.33 (q, 4 H, J = 7.2 Hz), 2.78-2.82 (m, 2 H), 1.34 (d, 6 H, J = 7.2 Hz), 1.18 (d, 12 H, J = 2.4 Hz). 13C NMR (100 MHz, CDCl3): δ = 165.32, 157.63, 144.01, 142.63, 127.13, 118.49, 76.14, 63.33, 59.20, 33.21, 23.95, 13.92. MS: m/z (%) = 605 (100) [M+], 428 (74), 385 (45), 287 (28), 202 (28), 146 (40), 132 (83).
Compound 4f: IR (KBr): 3411 (s), 1765 (s), 1722 (s), 1498 (m), 1468 (m), 1415 (s), 1238 (s), 1048 (m), 903 (m), 833 (m), 717 (m) cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.02 (d, 4 H, J = 8.8 Hz), 6.82 (d, 4 H, J = 8.8 Hz), 5.48 (d, 4 H, J = 14.0 Hz), 4.62 (d, 4 H, J = 14.0 Hz), 4.33 (q, 4 H, J = 7.2 Hz), 1.35 (t, 6 H, J = 7.2 Hz). 13C NMR (100 MHz, CDCl3): δ = 164.93, 157.10, 144.22, 129.21, 126.47, 118.46, 76.20, 63.53, 57.61, 13.87. MS: m/z (%) = 590 (100) [M+], 538 (21), 420 (70), 376 (27), 202 (25), 191 (9), 189 (21), 145 (65).
Compound 4g: IR (KBr): 3448 (m), 2981 (w), 2936 (w), 1746 (s), 1726 (s), 1496 (m), 1467 (m), 1417 (m), 1280 (m), 1239 (s), 1094 (m), 1047 (m), 975 (m), 908 (m), 818 (m) cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.18 (d, 4 H, J = 8.8 Hz), 6.77 (d, 4 H, J = 8.8 Hz), 5.48 (d, 4 H, J = 14.0 Hz), 4.62 (d, 4 H, J = 14.0 Hz), 4.34 (q, 4 H, J = 7.2 Hz), 1.35 (t, 6 H, J = 7.2 Hz). 13C NMR (100 MHz, CDCl3): δ = 164.87, 157.04, 144.77, 132.15, 118.88, 113.93, 76.16, 63.51, 57.53, 13.86. MS: m/z (%) = 679 (73) [M+], 467 (58), 466 (10), 464 (66), 423 (30), 420 (26), 409 (4), 243 (10), 241 (24), 240 (63), 182 (100).
Compound 4h: IR (KBr): 3426 (m), 1749 (s), 1727 (s), 1493 (m), 1466 (m), 1417 (m), 1279 (m), 1245 (s), 1174 (m), 1093 (m), 909 (m), 812 (m), 694 (m) cm-1. 1H NMR (400 MHz, CDCl3): δ = 7.37 (d, 4 H, J = 7.6 Hz), 6.66 (d, 4 H, J = 7.6 Hz), 5.47 (d, 4 H, J = 14.0 Hz), 4.61 (d, 4 H, J = 14.0 Hz), 4.33 (q, 4 H, J = 7.2 Hz), 1.34 (t, 6 H, J = 7.2 Hz). 13C NMR (100 MHz, CDCl3): δ = 164.95, 157.11, 145.62, 138.20, 119.46, 84.29, 76.24, 63.56, 57.62, 13.94. MS: m/z (%) = 723 (93) [M+], 647 (13), 513 (70), 387 (18), 231 (100), 208 (48).