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Novel reducing properties of a series of lanthanoid metals in the presence of SmI2

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Abstract

The reduction of dodecyl iodide, as model compound, with a series of lanthanoid (Ln) metals in the presence of catalytic amounts of samarium diiodide (SmI2) has been investigated in detail. The reducing activity of SmI2/Ln and the kinds of reduced products were found to be dependent on the individual Ln, but not on SmI2.

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Notes

  1. SmI2 is a useful reagent in organic synthesis, see, for example, Ref. [1].

  2. A THF solution of SmI2 has a deep blue color with absorption maxima at 565 and 617 nm, which can be assigned to a 4f 6 → 4f 55d1 transition [32].

  3. Most divalent species of Ln (LnI2) except SmI2 are less soluble in organic solvents, and, therefore, reduction of the oxidized surface of Ln metals with LnI2 is inefficient. In contrast, SmI2, which is soluble in THF, can efficiently reduce the oxidized surface of Ln metals. The reducing potential of SmI2 is −1.55 eV, whereas Ln metals have higher reducing potentials (−2.23 to −2.48 eV). Therefore, SmI2/Ln generally had greater reducing activity than LnI2/Ln.

  4. When SmI2 was used without Ln, 8 % of 2 was obtained; Ref. [42].

  5. Most of the unreacted starting material (1) was recovered. Formation of dodecyl anion was confirmed by quenching with ketone (Barbier reaction); Ref. [26].

References

  1. K.C. Nicolaou, S.P. Ellery, J.S. Chen, Angew. Chem. Int. Ed. 48, 7140 (2009)

    Article  CAS  Google Scholar 

  2. K. Gopalaiah, H.B. Kagan, New J. Chem. 32, 607 (2008)

    Article  CAS  Google Scholar 

  3. H.B. Kagan, Tetrahedron 59, 10351 (2003)

    Article  CAS  Google Scholar 

  4. Y. Sumino, A. Ogawa, J. Synth. Org. Chem Jpn. 61, 201 (2003)

    Article  CAS  Google Scholar 

  5. H.B. Kagan, J.L. Namy, in Topics in Organometallic Chemistry, vol. 2, ed. by S. Kobayashi (Springer, Berlin, 1999)

    Google Scholar 

  6. R. Nomura, T. Endo, Chem. Eur. J. 4, 1605 (1998)

    Article  CAS  Google Scholar 

  7. A. Krief, A.-M. Lavel, Acros Org. Acta 2, 17 (1996)

    CAS  Google Scholar 

  8. G.A. Molander, C.R. Harris, Chem. Rev. 96, 307 (1996)

    Article  CAS  Google Scholar 

  9. G.A. Molander, Chem. Rev. 92, 29 (1992)

    Article  CAS  Google Scholar 

  10. D.P. Curran, T.L. Fevig, C.P. Jasperse, M.J. Totleben, Synlett 1992, 943 (1992)

    Article  Google Scholar 

  11. A.J. Soderquist, Aldrichim. Acta 24, 15 (1991)

    CAS  Google Scholar 

  12. J. Inanaga, Rev. Heteroatom. Chem. 3, 75 (1990)

    Google Scholar 

  13. P. Grignard, J.L. Namy, H.B. Kagan, J. Am. Chem. Soc. 102, 2693 (1980)

    Article  Google Scholar 

  14. B.K. Banic, Eur. J. Org. Chem. 2431 (2002)

  15. J.M. Concellon, H. Rodriguez-Solla, E. Bardales, M. Huerta, Eur. J. Org. Chem. 1775 (2003)

  16. J.M. Concellon, P.L. Bernad, M. Huerta, S. Garcia-Granda, M.R. Diaz, Chem. Eur. J. 9, 5343 (2003)

    Article  CAS  Google Scholar 

  17. H. Rodriguez-Solla, E. Bardales, M. Huerta, Eur. J. Org. Chem. 1775 (2003)

  18. J.A. Teprovich Jr., P.K.S. Antharjanam, E. Prasad, E.N. Pesciotta, R.A. Flowers II, Eur. J. Inorg. Chem. 5015 (2008)

  19. Y. Tomisaka, K. Tsuchii, A. Ogawa, J. Alloys Compd. 408–412, 427 (2006)

    Article  Google Scholar 

  20. Z. Li, Y. Tomisaka, A. Nomoto, Y. Zhang, A. Ogawa, Chem. Lett. 38, 16 (2009)

    Article  Google Scholar 

  21. Y. Liu, Y. Zhang, Tetrahedron Lett. 45, 1295 (2004)

    Article  CAS  Google Scholar 

  22. Y. Liu, Y. Zhang, Tetrahedron 59, 8429 (2003)

    Article  CAS  Google Scholar 

  23. Y. Liu, X. Liu, Y. Zhang, Tetrahedron Lett. 44, 1667 (2003)

    Article  CAS  Google Scholar 

  24. Y. Liu, F. Zhang, Y. Qi, Y. Zhang, S. Zhang, Eur. J. Org. Chem. 5470 (2008)

  25. A. Ogawa, N. Takami, M. Sekiguchi, I. Ryu, N. Kambe, N. Sonoda, J. Am. Chem. Soc. 114, 8729 (1992)

    Article  CAS  Google Scholar 

  26. A. Ogawa, T. Nanke, N. Takami, Y. Sumino, I. Ryu, N. Sonoda, Chem. Lett. 23, 379 (1994)

    Google Scholar 

  27. A. Ogawa, N. Takami, T. Nanke, M. Sekiguchi, N. Kambe, N. Sonoda, Appl. Organomet. Chem. 9, 461 (1995)

    Article  CAS  Google Scholar 

  28. A. Ogawa, N. Takami, T. Nanke, S. Ohya, T. Hirao, N. Sonoda, Tetrahedron 53, 12895 (1997)

    Article  CAS  Google Scholar 

  29. I. Kamiya, K. Iida, N. Harato, Z. Li, Y. Tomisaka, A. Ogawa, J. Alloys Compd. 408–412, 437 (2006)

    Article  Google Scholar 

  30. Z. Li, K. Iida, Y. Tomisaka, A. Yoshimura, T. Hirao, A. Nomoto, A. Ogawa, Organometallics 26, 1212 (2007)

    Article  Google Scholar 

  31. A. Ogawa, Y. Sumino, I. Ryu, N. Kambe, N. Sonoda, Rare Earths 338 (1995)

  32. E. Prasad, B.W. Knettle, R.A. Flowers II, Chem. Eur. J. 11, 3105 (2005)

  33. A. Ogawa, T. Hirao, Y. Sumino, N. Sonoda, Rare Earths 298 (1996)

  34. W.G. Skene, J.C. Scaiano, F.L. Cozens, J. Org. Chem. 61, 7918 (1996)

    Article  CAS  Google Scholar 

  35. A. Ogawa, Y. Sumino, T. Nanke, S. Ohya, N. Sonoda, T. Hirao, J. Am. Chem. Soc. 119, 2745 (1997)

    Article  CAS  Google Scholar 

  36. A. Ogawa, S. Ohya, T. Hirao, Chem. Lett. 26, 275 (1997)

    Article  Google Scholar 

  37. A. Ogawa, S. Ohya, Y. Sumino, N. Sonoda, T. Hirao, Tetrahedron Lett. 38, 9017 (1997)

    Article  CAS  Google Scholar 

  38. A. Ogawa, S. Ohya, M. Doi, Y. Sumino, N. Sonoda, T. Hirao, Tetrahedron Lett. 39, 6341 (1998)

    Article  CAS  Google Scholar 

  39. Y. Sumino, N. Harato, Y. Tomisaka, A. Ogawa, Tetrahedron 59, 10499 (2003)

    Article  CAS  Google Scholar 

  40. Y. Tomisaka, N. Harato, M. Sato, A. Nomoto, A. Ogawa, Bull. Chem. Soc. Jpn. 79, 1444 (2006)

    Article  CAS  Google Scholar 

  41. A. Nomoto, Y. Kojo, G. Shiino, Y. Tomisaka, I. Mitani, M. Tatsumi, A. Ogawa, Tetrahedron Lett. 51, 6580 (2010)

    Article  CAS  Google Scholar 

  42. Y. Tomisaka, A. Nomoto, A. Ogawa, Tetrahedron Lett. 50, 584 (2009)

    Article  CAS  Google Scholar 

  43. S. Cotton, Lanthanide and Actinide Chemistry (Wiley, New York, 2006)

    Book  Google Scholar 

Download references

Acknowledgments

This research was supported by a Grant-in-Aid for Scientific Research, on Scientific Research (C, 23550057) from the Ministry of Education, Culture, Sports, Science and Technology, Japan, by the Industry-University Cooperation Program of Sakai City, and by the Kyoto-Advanced Nanotechnology Network.

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Authors and Affiliations

  1. Department of Applied Chemistry, Graduate School of Engineering, Osaka Prefecture University, 1-1 Gakuen-cho, Naka-ku, Sakai, Osaka, 599-8531, Japan

    Yuri Tomisaka, Aya Yoshimura, Akihiro Nomoto, Motohiro Sonoda & Akiya Ogawa

  2. Advanced Materials Research Laboratory, KRI, Inc., Kyoto Research Park, 134 Chudoji Minami-machi, Shimogyo-ku, Kyoto, 600-8813, Japan

    Yuri Tomisaka

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  1. Yuri Tomisaka
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  2. Aya Yoshimura
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  4. Motohiro Sonoda
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  5. Akiya Ogawa
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Correspondence to Akiya Ogawa.

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Tomisaka, Y., Yoshimura, A., Nomoto, A. et al. Novel reducing properties of a series of lanthanoid metals in the presence of SmI2 . Res Chem Intermed 39, 43–48 (2013). https://doi.org/10.1007/s11164-012-0630-x

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