1H-NMR analysis of copper-aminoglycoside complexes in solution and its implication for regioselective modification of multifunctional aminoglycoside antibiotics

Tetrahedron

Volumn 54, Issue 27, 1998, Pages 7705-7720

  Grapsas, Ioannis ^a   Massova, Irina ^a   Mobashery, Shahriar ^a  

^a WAYNE STATE UNIVERSITY   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

AMINOGLYCOSIDE ANTIBIOTIC AGENT; AMINOGLYCOSIDE DERIVATIVE; COPPER DERIVATIVE;

ARTICLE; CHEMICAL ANALYSIS; DRUG STRUCTURE; PRIORITY JOURNAL; PROTON NUCLEAR MAGNETIC RESONANCE; STEREOCHEMISTRY; STEREOSPECIFICITY; STRUCTURE ANALYSIS;

EID: 0032474723     PISSN: 00404020     EISSN: None     Source Type: Journal    
DOI: 10.1016/S0040-4020(98)00407-4     Document Type: Article

References (32)

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20. 1').
21. 1').
22. 1(dia) relaxation times were determined in the presence and absence of copper (II) acetate, respectively.
23. 15. The force-field parameters within the TRIPOS package were not developed specifically for the transition-metal complexes of aminosugars. The empirical molecular mechanic force-field methods usually give a qualitative measure of the energy contents of molecules, however, the reliability of the energy-minimized structures are high. We were compelled to use the TRIPOS force-field in light of the fact that to our knowledge this is the only force-field package that describes the parameters for coordination with cupric ion for complexes as large as the ones studied by us.
24. 16. Use of excess of di-t-butyldicarbonate does not affect lhe regiochemistry of the reaction. Excess of copper (II) acetate (4.0 equivs.) is, however, required in all cases. Reactions of kanamycin B (7) with excess di-t-butyldicarbonate at lower copper (II) acetate ratios showed that at least 3-fold excess of copper (II) acetate is needed for achieving the described regioselectivity.
25. 10c We found that other polar organic solvents could also be used without any effect on the regioselectivity of the reactions. For example, the reactions of neamine (8) and kanamycin B (7) with di-t-butyldicarbonate in the presence of the cupric ion were tried in methanol, which gave products identical to those obtained in DMSO. However, a crucial difference in the case of nucleophilic solvents is that the carbamoylating reagent is solvolized with metal ions serving as a catalyst, and a large excess of the reagent should therefore be used to bring the reaction to completion.
26. e values for protons of 6′-N-Boc-kanamycin A (26). These values (data not shown) were essentially identical to those of kanamycin A, and consequently the coordination patterns of these two compounds with the cupric ion were unaltered.
27. 23 revealed the existence of a hydrogen bond between the 1-amino and 2″-hydroxyl groups (a distance of 3.1 Å).
28. 20. Coordination, for example, of the cupric ion to the 2′-amino group of kanamycin B would diminish the probability of its hydrogen bonding to the 5-hydroxyl group, whereas this latter group would be more available for hydrogen bonding to 2″-bydroxyl group. In such a case the probability of a hydrogen bond between 2″-hydroxyt and the 1-amino group of kanamycin B would be diminished with respect to a similar hydrogen bond for kanamycin A.
29. 21. Allen, F. H.; Kennard, O. "3D Search and Research Using the Cambridge Structural Database" in Chemical Design Automation News, 1993, 8, pp. 1, 31-37.
30. 22. Mashaly, A. Polyhedron 1993, 12, 745.
31. 23. Koyama, G.; Iitaka, Y.; Maeda, K.; Umezawa, H. Tetrahedron Lett. 1968, 1875.
32. 21 all of which have coordinated heterogroups located in bulky substituents at axial positions. In the absence of metal, these structures should prefer equatorial arrangement for the 1-, 3-, and 5-substituents. However, coordination with the metal appears to stabilize the axial orientation for the substituents of the metal coordinated species.