On the regio- and stereoselective synthesis of aminocyclitols from cyclitol epoxides: The effect of Li as a chelating agent

Chemistry - A European Journal

Volumn 11, Issue 15, 2005, Pages 4465-4472

  Serrano, Pedro ^a,b   Llebaria, Amadeu ^b   Vázquez, Jordi ^c   De Pablo, Joan ^c,d   Anglada, Josep M ^b   Delgado, Antonio ^a,b  

^a UNIVERSITY OF BARCELONA   (Spain)

^b DEPARTMENT OF ENVIRONMENTAL CHEMISTRY   (Spain)

^c Centre Tecnologic de Manresa   (Spain)

^d UNIVERSITAT POLITÈCNICA DE CATALUNYA   (Spain)

Author keywords

Ab initio calculations; Amino alcohols; Conformation analysis; Epoxides; Regioselectivity

Indexed keywords

ALCOHOLS; CHELATION; CHROMATOGRAPHY; FILTRATION; LITHIUM COMPOUNDS; MATHEMATICAL MODELS; MODULATORS; NITROGEN; NUCLEAR MAGNETIC RESONANCE; SILICA GEL; SODIUM COMPOUNDS; SYNTHESIS (CHEMICAL);

AB INITIO CALCULATIONS; AMINO ALCOHOLS; CONFORMATION ANALYSIS; EPOXIDES; REGIOSELECTIVITY;

AMINES;

CHELATING AGENT; EPOXIDE; LITHIUM;

ARTICLE; CHEMISTRY; MASS SPECTROMETRY; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; STEREOISOMERISM;

CHELATING AGENTS; EPOXY COMPOUNDS; LITHIUM; MAGNETIC RESONANCE SPECTROSCOPY; MASS SPECTROMETRY; STEREOISOMERISM;

EID: 22944475824     PISSN: 09476539     EISSN: None     Source Type: Journal    
DOI: 10.1002/chem.200401270     Document Type: Article

References (43)

1. V. H. Lillelund, H. H. Jensen, X. F. Liang, M. Bols, Chem. Rev. 2002, 102, 515-553.
2. A. Berecibar, C. Grandjean, A. Siriwardena, Chem. Rev. 1999, 99, 779-844.
3. B. V. L. Potter, D. Lampe, Angew. Chem. 1995, 107, 2085-2125;
4. Angew. Chem. Int. Ed. Engl. 1995, 34, 1933-1972.
5. A. Delgado, P. Serrano, in XII Congreso National de la Sociedad Española de Quimica Terapéutica, Book of Abstracts, Sevilla, Spain, 2001, p. 61.
6. C. Jaramillo, J. Chiara, M. Martín-Lomas, J. Org. Chem. 1994, 59, 3135-3141.
7. P. Serrano, A. Llebaria, A. Delgado, J. Org. Chem. 2002, 67, 7165-7167.
8. 3 of related O-protected cyclophellitol derivatives, see: a) K. Tatsuta, S. Miura, Tetrahedron Lett. 1995, 36, 6721-6724;
9. b) S. Ogawa, N. Chida, T. Suami, J. Org. Chem. 1983, 48, 1203-1207; for reactions of cyclitol epoxides with amines, see;
10. c) R. A. Cadenas, M. Y. Grass, J. Mosettig, M. E. Gelpi, Nucleosides Nucleotides 1990, 9, 21-34;
11. d) S. Leicach, M. E. Gelpi, R. A. Cadenas, Nucleosides Nucleotides 1994, 13, 2051-2058.
12. M. Bartok, K. L. Lang, in Small Ring Heterocydes (Ed.: A. Hassner), Wiley, New York, 1985.
13. D. K. Murphy, R. L. Alumbaugh, B. Rickbom, J. Am. Chem. Soc. 1969, 91, 2649-2653.
14. a) E. L. Eliel, N. L. Allinger, S. J. Angyal, G. A. Morrison, in Conformational Analysis, Wiley, New York, 1965, p. 352;
15. b) P. Deslong-champs, Stereoelectronic effects in Organic Chemistry, Pergamon Press, Oxford, 1983;
16. c) J. Valls, E. Toromanoff, Bull. Soc. Chim. Fr. 1961, 758-764.
17. F. H. Newth, Q. Rev. Chem. Soc. 1959, 13, 30-47.
18. S. J. Angyal, Chem. Ind. (London) 1954, 1230-1231.
19. A. Furst, P. A. Plattner, Helv. Chim. Acta 1949, 32, 275-283.
20. F. Calvani, P. Crotti, C. Gardelli, M. Pineschi, Tetrahedron 1994, 50, 12999-13022, and references therein.
21. Experiments at RT failed to afford the opening adducts
22. In all cases, the regio- and the stereochemistry of the major adducts was confirmed from selected H-H coupling constants from azidoalcohols 3a and 4a. Moreover, in the case of 3a, symmetry considerations imposed by the meso nature of the azidoalcohol arising from trans-diaxial Cl opening of epoxide 1 were conclusive.
23. 4 led to precipitation.
24. 1H NMR pattern of the cyclohexane moiety, since dihedral angles should be significantly different for both limit conformations (A1 and E1). Thus, high J values would be indicative of any of the "all-equatorial" conformations, whereas small J values would be expected for the "all-axial" one.
25. E. M. Cabaleiro-Lago, M. A. Ríos, Chem. Phys. 2000, 254, 11-23.
26. A. D. Becke, J. Chem. Phys. 1993, 98, 5648-5652.
27. J. Tomasi, B. Mennucci, E. Cancés, J. Mol. Struct. 1999, 464, 211-226.
28. B. Mennucci, J. Tomasi, J. Chem. Phys. 1997, 106, 5151-5158.
29. R. F. W. Bader, Atoms in Molecules. A Quantum Theory, Clarendon Press, Oxford, UK, 1990.
30. J. Clayden, N. Greeves, S. Warren, P. Wothers, Organic Chemistry, 1st ed., Oxford University Press, Oxford, 2001.
31. 4 solution. On the other side, the above experimental requirements would be consistent with the participation of three Li ions that could chelate the "all-equatorial" conformer. This possibility was taken into account and despite the corresponding transition states for the C1 and C2 attack have been found, we could not obtain the optimised geometries for the corresponding pre-reactive complexes. However, form an energetic standpoint, the transition state describing the C1 attack also lie below in energy than that corresponding to the C2 attack, in agreement with the experimental findings.
32. A. Streitwieser, M. Husemann, Y.-J. Kim, J. Org. Chem. 2003, 68, 7937-7942.
33. L. A. Paquette, C. S. Ra, J. C. Gallucci, H.-J. Kang, N. Ohmori, M. P. Arrington, W. David, J. S. Brodbelt, J. Org. Chem. 2001, 66, 8629-8639.
34. L. A. Paquette, J. Tae, J. Am. Chem. Soc. 2001, 123, 4974-4984.
35. L. A. Paquette, J. Tae, J. C. Gallucci, Org. Lett. 2000, 2, 143-146.
36. J. Tae, R. D. Rogers, L. A. Paquette, Org. Lett. 2000, 2, 139-142.
37. L. A. Paquette, J. Tae, E. R. Hickey, R. D. Rogers, Angew. Chem. 1999, 111, 1502-1505;
38. Angew. Chem. Int. Ed. Angew. Chem. Int. Ed. Engl. 1999, 38, 1409-1411.
39. Experimental conditions require heating at 80°C to revert the preferred coordination of Li ion with acetonitrile. (see ref. [19]).
40. P. C. Hariharan, J. A. Pople, Theor. Chim. Acta 1973, 28, 213-222.
41. M. J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewsk, J. J. A. Montgomery, R. E. Stratmann, J. C. Buran, S. Dapprich, J. M. Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi, V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S. Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma, N. Rega, P. Salvador, J. J. Dannenberg, D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J. Cioslowski, V. Ortiz, A. G. Baboul, B. B. Stefanov, A. L. G. Liu, P. Piskorz, I. Komaromi, R. G. L. Martin, D. J. Fox, T. Keith, M. A. Al-Laham, C. Y. Peng, A. Nanayakkara, M. Challacombe, P. M. W. Gill, B. Johnson, M. W. W. W. Chen, J. L. Andres, C. Gonzalez, M. Head-Gordon, E. S. Replogle, J. A. Pople, Gaussian, Inc., Pittsburgh PA, 2002.
42. R. F. W. Bader, http://www.chemistry.mcmaster.ca/aimpac, down-loaded May 2002.
43. G. Schaftenaar, CAOS/CAMM Center, The Netherlands, 2002.