Remarkably facile ring-size control in macrocyclization: Synthesis of hemicucurbit[6]uril and hemicucurbit[12]uril

Angewandte Chemie - International Edition

Volumn 43, Issue 38, 2004, Pages 5019-5022

  Miyahara, Yuji ^a   Goto, Kenta ^a   Oka, Masakazu ^a   Inazu, Takahiko ^a  

^a KYUSHU UNIVERSITY   (Japan)

Author keywords

Cyclization; Gels; Host guest systems; Inclusion compounds; Macrocycles

Indexed keywords

CHEMICAL COMPOUNDS; CONCENTRATION (PROCESS); CONDENSATION; GELATION; HYDROCHLORIC ACID;

GELATING AGENTS; HCL CONCENTRATION; MACROCYCLIZATION;

SYNTHESIS (CHEMICAL);

CARBONYL DERIVATIVE; CATION; CHLOROFORM; DIETHYLENE GLYCOL; ETHYLENE; ETHYLENE GLYCOL; FORMALDEHYDE; HEMICUCURBIT[12]URIL; HEMICUCURBIT[6]URIL; IMIDAZOLIDINONE; MACROCYCLIC COMPOUND; METAL DERIVATIVE; OLIGOMER; ORGANIC SOLVENT; OXYGEN; POLYMER; PROPYLENE GLYCOL; THIOCYANATE; THIOCYANIC ACID DERIVATIVE; UNCLASSIFIED DRUG; UREA DERIVATIVE;

AB INITIO CALCULATION; ARTICLE; CHEMICAL COMPOSITION; CONFORMATION; CRYSTAL STRUCTURE; CYCLIZATION; DEPOLYMERIZATION; DERIVATIZATION; GEL PERMEATION CHROMATOGRAPHY; HYDROGEN BOND; HYDROPHOBICITY; MASS SPECTROMETRY; MOLECULAR INTERACTION; MOLECULAR WEIGHT; MONTE CARLO METHOD; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; OSMOLALITY; PH; POLYMERIZATION; SUPRAMOLECULAR CHEMISTRY; SYNTHESIS; VISCOSITY; X RAY ANALYSIS; X RAY CRYSTALLOGRAPHY; X RAY DIFFRACTION;

BRIDGED COMPOUNDS; CRYSTALLOGRAPHY, X-RAY; CYCLIZATION; IMIDAZOLES; MACROCYCLIC COMPOUNDS; MODELS, MOLECULAR; MOLECULAR CONFORMATION;

EID: 4944227839     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200460764     Document Type: Article

References (21)

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4. The complexation of Cuc6 with a variety of metal salts was studied without knowing its structure, see R. Behrend, E. Meyer, F. Rusche, Justus Liebigs Ann. Chem. 1905, 339, 1-37; for recent studies, see H.-J. Buschmann, E. Cleve, E. Schollmeyer, Inorg. Chim. Acta 1992, 193, 93-97 for Cuc6 and X. X. Zhang, K. E. Krakowiak, G. Xue, J. S. Bradshaw, R. M. Izatt, Ind. Eng. Chem. Res. 2000, 39, 3516-3520 for MeCuc5.
5. The complexation of Cuc6 with a variety of metal salts was studied without knowing its structure, see R. Behrend, E. Meyer, F. Rusche, Justus Liebigs Ann. Chem. 1905, 339, 1-37; for recent studies, see H.-J. Buschmann, E. Cleve, E. Schollmeyer, Inorg. Chim. Acta 1992, 193, 93-97 for Cuc6 and X. X. Zhang, K. E. Krakowiak, G. Xue, J. S. Bradshaw, R. M. Izatt, Ind. Eng. Chem. Res. 2000, 39, 3516-3520 for MeCuc5.
6. The complexation of Cuc6 with a variety of metal salts was studied without knowing its structure, see R. Behrend, E. Meyer, F. Rusche, Justus Liebigs Ann. Chem. 1905, 339, 1-37; for recent studies, see H.-J. Buschmann, E. Cleve, E. Schollmeyer, Inorg. Chim. Acta 1992, 193, 93-97 for Cuc6 and X. X. Zhang, K. E. Krakowiak, G. Xue, J. S. Bradshaw, R. M. Izatt, Ind. Eng. Chem. Res. 2000, 39, 3516-3520 for MeCuc5.
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10. b) G. Camino, M.P. Luda, L. Costa, M. Guaita, Macromol. Chem. Phys. 1996, 197, 41-60.
11. For the conditions and mechanisms of the Cucurbituril synthesis, see a) A. Day, A. F. Arnold, R. J. Blanch, B. Snushall, J. Org. Chem. 2001, 66, 8094-8100;
12. b) A. Chakraborty, A. Wu, D. Witt, J. Lagona, J. C. Fettinger, L. Isaacs, J. Am. Chem. Soc. 2002, 124, 8297-8306.
13. The properties and X-ray analyses of the compounds reported are given in the Supporting Information.
14. 3 led to precipitation of the complex.
15. The usual conformational search using molecular mechanics appears unreliable for polar urea derivatives. The B3LYP/STO-3G optimized structure is the best we could find so far, but the conformational problem in solution is apparently much more complex because of the flexibility and polar interactions. Internal thermal motion as found in supercoiled DNA may also be possible in this large macrocycle. For internal motion, see A. Stasiak in Large Ring Molecules (Ed.: J. A. Semlyen), Wiley, Chichester, UK, 1996, pp. 43-97.
16. For a variety of natural and synthetic macrocycles, see, Large Ring Molecules (Ed.: J. A. Semlyen), Wiley, Chichester, UK, 1996. There seems to be no prior examples for such an efficient control of macrocyclization.
17. N2 condensation, particularly when benzimidazol-2-one units are included; see J. Trepte, M. Czugler, K. Gloe, E. Weber, Chem. Commun. 1997, 1461-1462; S. Kumar, D. Paul, G. Hundal, M. S. Hundal, H. Singh, J. Chem. Soc. Perkin Trans. 1 2000, 1037-1043; Z. Shi, R. P. Thummel, Tetrahedron Lett. 1995, 36, 2741-2744; O. Meth-Cohn, Z. Yan, J. Chem. Soc. Perkin Trans. 1 1998, 423-436. Benzimidazol-2-one proved to be much less reactive in its condensation with formaldehyde than ethyleneurea under acidic conditions, Trimethyleneurea units have also been utilized in macrocyclic hosts: J. A. Bryant, S. P. Ho, C. B. Knobler, D. J. Cram, J. Am. Chem. Soc. 1990, 112, 5837-5843, and references therein. Trimethyleneurea, though reactive with formaldehyde under acidic conditions, failed to give readily identifiable products.
18. N2 condensation, particularly when benzimidazol-2-one units are included; see J. Trepte, M. Czugler, K. Gloe, E. Weber, Chem. Commun. 1997, 1461-1462; S. Kumar, D. Paul, G. Hundal, M. S. Hundal, H. Singh, J. Chem. Soc. Perkin Trans. 1 2000, 1037-1043; Z. Shi, R. P. Thummel, Tetrahedron Lett. 1995, 36, 2741-2744; O. Meth-Cohn, Z. Yan, J. Chem. Soc. Perkin Trans. 1 1998, 423-436. Benzimidazol-2-one proved to be much less reactive in its condensation with formaldehyde than ethyleneurea under acidic conditions, Trimethyleneurea units have also been utilized in macrocyclic hosts: J. A. Bryant, S. P. Ho, C. B. Knobler, D. J. Cram, J. Am. Chem. Soc. 1990, 112, 5837-5843, and references therein. Trimethyleneurea, though reactive with formaldehyde under acidic conditions, failed to give readily identifiable products.
19. N2 condensation, particularly when benzimidazol-2-one units are included; see J. Trepte, M. Czugler, K. Gloe, E. Weber, Chem. Commun. 1997, 1461-1462; S. Kumar, D. Paul, G. Hundal, M. S. Hundal, H. Singh, J. Chem. Soc. Perkin Trans. 1 2000, 1037-1043; Z. Shi, R. P. Thummel, Tetrahedron Lett. 1995, 36, 2741-2744; O. Meth-Cohn, Z. Yan, J. Chem. Soc. Perkin Trans. 1 1998, 423-436. Benzimidazol-2-one proved to be much less reactive in its condensation with formaldehyde than ethyleneurea under acidic conditions, Trimethyleneurea units have also been utilized in macrocyclic hosts: J. A. Bryant, S. P. Ho, C. B. Knobler, D. J. Cram, J. Am. Chem. Soc. 1990, 112, 5837-5843, and references therein. Trimethyleneurea, though reactive with formaldehyde under acidic conditions, failed to give readily identifiable products.
20. N2 condensation, particularly when benzimidazol-2-one units are included; see J. Trepte, M. Czugler, K. Gloe, E. Weber, Chem. Commun. 1997, 1461-1462; S. Kumar, D. Paul, G. Hundal, M. S. Hundal, H. Singh, J. Chem. Soc. Perkin Trans. 1 2000, 1037-1043; Z. Shi, R. P. Thummel, Tetrahedron Lett. 1995, 36, 2741-2744; O. Meth-Cohn, Z. Yan, J. Chem. Soc. Perkin Trans. 1 1998, 423-436. Benzimidazol-2-one proved to be much less reactive in its condensation with formaldehyde than ethyleneurea under acidic conditions, Trimethyleneurea units have also been utilized in macrocyclic hosts: J. A. Bryant, S. P. Ho, C. B. Knobler, D. J. Cram, J. Am. Chem. Soc. 1990, 112, 5837-5843, and references therein. Trimethyleneurea, though reactive with formaldehyde under acidic conditions, failed to give readily identifiable products.
21. N2 condensation, particularly when benzimidazol-2-one units are included; see J. Trepte, M. Czugler, K. Gloe, E. Weber, Chem. Commun. 1997, 1461-1462; S. Kumar, D. Paul, G. Hundal, M. S. Hundal, H. Singh, J. Chem. Soc. Perkin Trans. 1 2000, 1037-1043; Z. Shi, R. P. Thummel, Tetrahedron Lett. 1995, 36, 2741-2744; O. Meth-Cohn, Z. Yan, J. Chem. Soc. Perkin Trans. 1 1998, 423-436. Benzimidazol-2-one proved to be much less reactive in its condensation with formaldehyde than ethyleneurea under acidic conditions, Trimethyleneurea units have also been utilized in macrocyclic hosts: J. A. Bryant, S. P. Ho, C. B. Knobler, D. J. Cram, J. Am. Chem. Soc. 1990, 112, 5837-5843, and references therein. Trimethyleneurea, though reactive with formaldehyde under acidic conditions, failed to give readily identifiable products.