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Small-ring heterocycles as components of multidentate ligands: some structural studies relating to ring opening

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Abstract

Structural studies of seven complexes of ligands derived from various azetidine- and oxetane-containing ligands characterise the difference in reactivity of both free and bound forms of these two four-membered heterocycles. The relatively unreactive azetidine ring is preserved in a variety of transformations, whereas facile opening of the oxetane ring provides a convenient pathway to complexes with pendent functionality.

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Notes

  1. Where the coordination preferences of the metal ion are such that this binding is not favoured, the ligand, bound quadridentate in a square-planar species, appears to prefer the common, cyclam-like conformation where both six-membered chelate rings adopt the chair conformation [33]

References

  1. Banks, H.D.: Torquoselectivity studies in the generation of azomethine ylides from substituted aziridines. J. Org. Chem. 75, 2510–2517 (2010)

    Article  CAS  Google Scholar 

  2. Métro, T.-X., Duthion, B., Pardo, D.G., Cossy, J.: Rearrangement of β-amino alcohols via aziridiniums: a review. Chem. Soc. Rev. 39, 89–102 (2010)

    Article  Google Scholar 

  3. Loy, R.N., Jacobsen, E.N.: Enantioselective intramolecular openings of oxetanes catalyzed by (salen)Co(III) complexes: access to enantioenriched tetrahydrofurans. J. Am. Chem. Soc. 131, 2786–2787 (2009)

    Article  CAS  Google Scholar 

  4. Dwivedi, S.K., Gandhi, S., Rastogi, N., Singh, V.K.: Lewis acid catalyzed regioselective ring opening of azetidines with alcohols and thiols. Tetrahedron Lett. 48, 5375–5377 (2007)

    Article  CAS  Google Scholar 

  5. Hu, X.E.: Nucleophilic ring opening of aziridines. Tetrahedron 60, 2701–2743 (2004). and references therein

    Article  CAS  Google Scholar 

  6. Murahashi, S.-I., Yoshimura, N., Tsumiyama, T., Kajima, T.: Catalytic alkyl group exchange reaction of primary and secondary amines. J. Am. Chem. Soc. 105, 5002–5011 (1983)

    Article  CAS  Google Scholar 

  7. Garrett, A.D., White, P.S., Templeton, J.L.: Coordination and derivatization of 3,4, and 6-membered nitrogen heterocycles at a chiral tungsten(II) center. Inorg. Chim. Acta 361, 3135–3148 (2008). and references therein

    Article  CAS  Google Scholar 

  8. Lorenz, I.P., von Beckerath, S., Nöth, H.: Aziridines as complex ligands: coordination and ring opening. Eur. J. Inorg. Chem. 645–650 (1988)

  9. Adams, R.D., Chen, G.: The coordination and activation of azetidine by a triosmium cluster. Organometallics 12, 2070–2077 (1993)

    Article  CAS  Google Scholar 

  10. Ware, D.C., Siim, B.G., Robinson, K.G., Denny, W.A., Brothers, P.J., Clark, G.R.: Synthesis and characterization of aziridine complexes of cobalt(III) and chromium(III) designed as hypoxia-selective cytotoxins. X-ray crystal structure of trans-[Co(Az)4(NO2)2]Br·2H2O·LiBr. Inorg. Chem. 30, 3750–3757 (1991)

    Article  CAS  Google Scholar 

  11. Singh, M.M., Angelici, R.J.: Reactions of aziridine, oxirane, and thiirane with carbonyl and thiocarbonyl ligands in complexes of iron, manganese, and ruthenium: syntheses of cyclic carbene compounds. Inorg. Chem. 23, 2691–2698 (1984)

    Article  CAS  Google Scholar 

  12. King, R.B., Von Stetten, O.: Complexes of trivalent phosphorus derivatives. XVI. Metal complexes of some aziridinophosphines related to anticancer drugs. Inorg. Chem. 13, 2449–2453 (1974)

    Article  CAS  Google Scholar 

  13. Buckingham, D.A., Davis, C.E., Sargeson, A.M.: Cobalt(III)-promoted lysis at saturated carbon. Examples of internalucleophilic displacement. J. Am. Chem. Soc. 92, 6159–6170 (1970)

    Article  CAS  Google Scholar 

  14. Jackson, T.B., Edwards, J.O.: Coördination compounds of labile metals with ethylenimine. J. Am. Chem. Soc. 83, 355–360 (1961)

    Article  CAS  Google Scholar 

  15. Lee, Y.H., Harrowfield, J.M., Kim, Y., Lim, W.T., Park, Y.C., Thuéry, P.: Functionalised azetidines as ligands: pyridyl-complemented coordination. Dalton Trans. 434–442 (2009)

  16. Lee, Y.H., Harrowfield, J.M., Kim, J.S., Kim, Y., Lee, M.H., Lim, W.T., Park, Y.C., Thuéry, P.: Functionalised azetidines as ligands: species derived by selective alkylation at substituent-nitrogen. Dalton Trans. 443–454 (2009)

  17. Lee, D.-H., Lee, Y.H., Harrowfield, J.M., Lee, I.-M., Lee, H.I., Lim, W.T., Kim, Y., Jin, M.-J.: Phosphine-free sonogashira coupling: reactions of aryl halides catalyzed by palladium(II) complexes of azetidine-derived polyamines under mild conditions. Tetrahedron 65, 1630–1634 (2009)

    Article  CAS  Google Scholar 

  18. Comba, P., Dovalil, N., Kim, H.H., Kim, J.S., Kim, Y., Lee, Y.H., Thuéry, P., Zajaczkowski, M.: Synthesis, solid state and solution structures of two isomeric dicopper(II) complexes with functionalized azetidine ligands. J. Incl. Phenom. Macrocycl. Chem. 65, 59–64 (2009)

    Article  CAS  Google Scholar 

  19. Lee, Y.H., Kim, H.H., Thuéry, P., Harrowfield, J.M., Lim, W.T., Kim, Y.: Functionalised azetidines as ligands: some basic coordination chemistry. J. Incl. Phenom. Macrocycl. Chem. 65, 65–71 (2009)

    Article  CAS  Google Scholar 

  20. Lee, D.-H., Lee, Y.H., Kim, D.I., Kim, Y., Lim, W.T., Harrowfield, J.M., Thuéry, P., Kim, M.-J., Park, Y.C., Lee, I.-M.: A highly effective azetidine—Pd(II) catalyst for Suzuki—Miyaura coupling reactions in water. Tetrahedron 64, 7178–7182 (2008)

    Article  CAS  Google Scholar 

  21. Bernhardt, P.V., Harrowfield, J.M., Kim, Y., Lee, Y.H., Park, Y.C., Sujandi, : A functionalised macrobicycle complex available for surface immobilisation and protein grafting. Bull. Korean Chem. Soc. 28, 589–595 (2007)

    Article  CAS  Google Scholar 

  22. Bernhardt, P.V., Kim, Y., Sujandi, : Cobalt complexes of tripodal hexadentate ligands: electrochemically driven rearrangements. Aust. J. Chem. 59, 783–790 (2006)

    Article  CAS  Google Scholar 

  23. Bernhardt, P.V., Cho, J.H., Harrowfield, J.M., Kim, J.Y., Kim, Y., Sujandi, Thuéry, P., Yoon, D.C.: Polyamines from polyols—pathways to azamacrocycles with hydroxymethyl pendent groups. Polyhedron 25, 1811–1822 (2006)

    Article  CAS  Google Scholar 

  24. Harrowfield, J.M., Kim, J.Y., Kim, Y., Lee, Y.H., Thuéry, P.: Coordination chemistry of Co(III) complexes of an azetidine-derived quadridentate amine and a related macrocycle. Polyhedron 24, 1569–1576 (2005)

    Article  CAS  Google Scholar 

  25. Bernhardt, P.V., Harrowfield, J.M., Kim, Y., Koutsantonis, G.A., Lee, Y.H., Thuéry, P.: Functionalized macrocycles from functionalized tetra-amines: pendent-arm macrocycles derived from dichloropivalic acid. Inorg. Chem. 43, 1681–1688 (2004)

    Article  CAS  Google Scholar 

  26. Harrowfield, J.M., Jang, G., Kim, Y., Thuéry, P., Vicens, J.: Azetidines as intermediates in polyamine synthesis—structure and reactions of a quadridentate ligand incorporating an azetidine ring. J. Chem. Soc. Dalton Trans. 1241–1243 (2002)

  27. Fabbrizzi, L., Licchelli, M., Mosca, L., Poggi, A.: Template synthesis of azacyclam metal complexes using primary amides as locking fragments. Coord. Chem. Rev. 254, 1628–1636 (2010)

    Article  CAS  Google Scholar 

  28. Bernhardt, P.V., Lawrance, G.A.: Complexes of polyaza macrocycles bearing pendent coordinating groups. Coord. Chem. Rev. 104, 297–343 (1990)

    Article  CAS  Google Scholar 

  29. Comba, P., Jurisic, P., Lampeka, Y.D., Peters, A., Prikhod’ko, A.I., Pritzkow, H.: Axial bonds in copper(II) compounds. Inorg. Chim. Acta 324, 99–107 (2001)

    Article  CAS  Google Scholar 

  30. Harrowfield, J.M., Kim, J.Y., Kim, Y., Lee, Y.H., Sujandi, Thuéry, P.: Podand hexamines and the synthesis of pendent-arm tetra-azamacrocycles. Polyhedron 24, 968–975 (2005)

    Article  CAS  Google Scholar 

  31. Harrowfield, J.M., Kim, Y., Koutsantonis, G.A., Lee, Y.H., Thuéry, P.: Stereochemistry in functionalized macrocycle complexes: control of hydroxyl substituent orientation. Inorg. Chem. 43, 1689–1696 (2004)

    Article  CAS  Google Scholar 

  32. Choi, M-H., Harrowfield, J.M., Kim, B.J., Kim, I-C., Kim, S-H., Kim, Y., Lee, M-K., Mocerino, M., Rukmini, E., Skelton, B.W., White, A.H.: Inter- and intra-molecular pathways in polyamine synthesis from diamine. J. Chem. Soc. Dalton Trans. 707–722 (2001)

  33. Bosnich, B., Poon, C.K., Tobe, M.L.: Complexes of cobalt(III) with a cyclic tetradentate secondary amine. Inorg. Chem. 4, 1102–1108 (1965)

    Article  CAS  Google Scholar 

  34. Dorofeeva, O.V., Mastryukov, V.S., Vilkov, L.V.: Ring puckering of azetidine: an electron diffraction study. J. Chem. Soc. Chem. Commun. 722a–772a (1973)

  35. Bond, A.D., Davies, J.E., Parsons, S.: Azetidine, pyrrolidine and hexamethyleneimine at 170 K. Acta Cryst C64, o543–o546 (2008)

    CAS  Google Scholar 

  36. Day, G.M., Motherwell, W.D.S., Ammon, H.L., Boerrigter, S.X.M., Della Valle, R.G., Venuti, E., Dzyabchenko, A., Dunitz, J.D., Schweizer, B., van Eijck, B.P., Erk, P., Facelli, J.C., Bazterra, V.E., Ferraro, M.B., Hofmann, D.W.M., Leusen, F.J.J., Liang, C., Pantelides, C.C., Karamertzanis, P.G., Price, S.L., Lewis, T.C., Nowell, H., Torrisi, A., Scheraga, H.A., Arnautova, Y.A., Schmidt, M.U., Verwer, P.: A third blind test of crystal structure prediction. Acta Cryst B61, 511–527 (2005)

    CAS  Google Scholar 

  37. Gahan, L.R., Hambley, T.W.: Synthesis, structures, and spectra of cobalt(III) complexes of the novel branched cyclic ligands 6-methyl-6-(4-amino-2-azabutyl)-1-thia-4-azacycloheptane and N-(2-aminoethyl)-3-methyl-3-(4-amino-2-thiabutyl)azetidine. Inorg. Chem. 26, 2532–2537 (1987)

    Article  CAS  Google Scholar 

  38. Geue, R.J., McCarthy, M.G., Sargeson, A.M., Jorgensen, P., Hazell, R.G., Larsen, F.K.: Synthesis and properties of novel cobalt(III) and nickel(II) complexes with coordinated azetidine nitrogens: crystal structure of mer-tris(3-aminomethyl)-3-methylazetidine)cobalt(III) chloride. Inorg. Chem. 24, 2559–2565 (1985)

    Article  CAS  Google Scholar 

  39. Keller, L., Sanchez, M.V., Prim, D., Couty, F., Evano, G., Marrot, J.: Azetidines as ligands in the Pd(II) complexes series. J. Organomet. Chem. 690, 2306–2311 (2005)

    Article  CAS  Google Scholar 

  40. Comba, P., Kerscher, M.: Structure correlation in bispidine coordination compounds—isomerism and tuneable reactivity. Cryst. Eng. 6, 197–211 (2003)

    Article  CAS  Google Scholar 

  41. Juran, S., Walther, M., Stephan, H., Bergmann, R., Steinbach, J., Kraus, W., Emmerling, F., Comba, P.: Exadentate bispidine derivatives as versatile bifunctional chelate agents for copper(II) radioisotopes. Bioconjugate Chem. 20, 347–359 (2009)

    Article  CAS  Google Scholar 

  42. Lesma, G., Pilati, T., Sacchetti, A., Silvani, A.: New chiral diamino ligands as sparteine analogues. Application to the palladium-catalyzed kinetic oxidative resolution of 1-phenyl ethanol. Tetrahedron Asymmetr. 19, 1363–1366 (2008)

    Article  CAS  Google Scholar 

  43. Blackman, A.: Overcoming the chelate effect: hypodentate coordination of common multidentate amine ligands. C. R. Chimie 8, 107–119 (2005)

    Article  CAS  Google Scholar 

  44. Anet, F.A.L.: On the reported high barrier to nitrogen inversion in azetidine (trimethylenimine). J. Am. Chem. Soc. 107, 4335 (1985)

    Article  CAS  Google Scholar 

  45. Geue, R.J., Hambley, T.W., Harrowfield, J.M., Sargeson, A.M., Snow, M.R.: Metal ion encapsulation: cobalt cages derived from polyamines, formaldehyde, and nitromethane. J. Am. Chem. Soc. 106, 5478–5488 (1984)

    Article  CAS  Google Scholar 

  46. Bernhardt, P.V., Jones, L.A.: Electrochemistry of macrocyclic cobalt(III/II) hexaamines: electrocatalytic hydrogen evolution in aqueous solution. Inorg. Chem. 38, 5086–5090 (1999). and references therein

    Article  CAS  Google Scholar 

  47. Boerzel, H., Comba, P., Prtizkow, H., Sickmüller, A.F.: Preparation, structure, and electronic properties of a low-spin iron(II) hexaamine compound. Inorg. Chem. 37, 3853–3857 (1998)

    Article  CAS  Google Scholar 

  48. Lawrance, G.A., Lye, P.G.: Pseudo-encapsulation: open prison ligands for metal ions. Comments Inorg. Chem. 15, 339–368 (1994)

    Article  CAS  Google Scholar 

  49. Harrowfield, J.M., Norris, V., Sargeson, A.M.: Reactivity of coordinated nucleophiles. A comparison of metal bound imidazolate and hydroxide ions as models for carbonic anhydrase. J. Am. Chem. Soc. 98, 7282–7289 (1976). and references therein

    Article  CAS  Google Scholar 

  50. Steed, J.W., Goeta, A.E., Lipkowski, J., Swierczynski, D., Panteleon, V., Handa, S.: Templated crystal nucleation: Mixed crystals of very different copper(II) N,N′,N″-trimethyltriazacyclononane complexes. Chem. Commun. 813–815 (2007)

  51. Ghorai, M.N., Kumar, A., Das, K.: Lewis acid-mediated unprecedented ring-opening rearrangement of 2-aryl-N-tosylazetidines to enantiopure (E)-allylamines. Org. Lett. 9, 5441–5444 (2007)

    Article  CAS  Google Scholar 

  52. Börzel, C.H., Comba, P., Hagen, K.S., Kerscher, M., Pritzkow, H., Schatz, M., Schindler, S., Walter, O.: Copper-bispidine coordination chemistry: syntheses, structures, solution properties, and oxygenation reactivity. Inorg. Chem. 41, 5440–5452 (2002)

    Article  Google Scholar 

  53. Hooft, R.W.W.: COLLECT. Nonius BV, Delft, The Netherlands (1998)

    Google Scholar 

  54. Otwinowski, Z., Minor, W.: Processing of X-ray diffraction data collected in oscillation mode. Methods Enzymol. 276, 307–326 (1997)

    Article  CAS  Google Scholar 

  55. Sheldrick, G.M.: A short history of SHELX. Acta Crystallogr. A 64, 112–122 (2008)

    Article  Google Scholar 

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Acknowledgment

This research was supported by the National Research Foundation of Korea (Grant 2010-0016624).

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Authors and Affiliations

  1. Department of Chemistry & Advanced Materials, Kosin University, 149-1, Dongsam-dong, Yeongdo-gu, Busan, 606-701, South Korea

    Young Hoon Lee, Mihyun Kim, A Rim Woo & Yang Kim

  2. Department of Chemistry, College of Natural Science, Jeju National University, Jeju, 690-756, South Korea

    Ji Young Choi & Jong Chul Byun

  3. Institut de Science et d’Ingénierie Supramoléculaires, Université de Strasbourg, 8, allée Gaspard Monge, 67083, Strasbourg, France

    Jack M. Harrowfield

  4. Department of Applied Chemistry, Andong National University, Andong, Kyungpook, South Korea

    Woo Taik Lim

  5. CEA, IRAMIS, UMR 3299 CEA/CNRS SIS2M, LCCEf, Bâtiment 125, 91191, Gif-sur-Yvette, France

    Pierre Thuéry

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  1. Young Hoon Lee
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Correspondence to Yang Kim.

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Dedicated to Professor Leonard F. Lindoy, the “compleat coordination chemist” and master of macrocycles, on the occasion of his 75th birthday.

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Lee, Y.H., Kim, M., Woo, A.R. et al. Small-ring heterocycles as components of multidentate ligands: some structural studies relating to ring opening. J Incl Phenom Macrocycl Chem 71, 395–407 (2011). https://doi.org/10.1007/s10847-011-9931-8

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