Skip to main content
Log in

Transfer of methylene groups promoted by metal complexation

  • Letter
  • Published:

From Nature

View current issue Submit your manuscript

Abstract

SELECTIVE chemical transformations involving hydrocarbons are a major goal in synthetic chemistry. Transition-metal complexes are capable of promoting a range of selective transformations of organic molecules under mild conditions1,2, and much effort has been devoted to studying their reactivity towards hydrocarbons3–7. Here we report a reaction promoted by a rhodium complex in which a methylene (CH2) group can be abstracted from a methyl (CH3) group and inserted into a variety of bonds, such as Si-H, Si-Si and C-H. Our approach presently requires a certain coordination geometry in the metal complex, involving chelation of the metal centre, but we believe that it can be extended to other substrates capable of metal coordination and may eventually lead to a general strategy for CH2 transfer from hydrocarbons to other molecules under mild conditions.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Similar content being viewed by others

References

  1. Collman, J. P., Hegedus, L. S., Norton, J. R. & Finke, R. G. Principles and Applications of Organotransition Metal Chemistry (University Science Books, Mill Valley, California, 1987).

    Google Scholar 

  2. Parshall, G. W. & Ittel, S. D. Homogeneous Catalysis 2nd edn (Wiley, New York, 1992).

    Google Scholar 

  3. Bergman, R. G. Science 223, 902–908 (1984).

    Article  CAS  ADS  Google Scholar 

  4. Crabtree, R. H. Chem. Rev. 85, 245–269 (1985).

    Article  CAS  Google Scholar 

  5. Jones, W. D. in Selective Hydrocarbon Activation (eds Davies, J. A., Watson, P. L., Liebman, J. F. & Greenberg, A.) 113–145 (VCH, New York, 1990).

    Google Scholar 

  6. Murai, S. et al. Nature 366, 529–531 (1993).

    Article  CAS  ADS  Google Scholar 

  7. Gozin, M., Weisman, A., Ben-David, Y. & Milstein, D. Nature 364, 699–701 (1993).

    Article  CAS  ADS  Google Scholar 

  8. Ojima, I. in The Chemistry of Organic Silicon Compounds (eds Patai, S. & Rappoport, Z.) 1479–1526 (Wiley, New York, 1989).

    Book  Google Scholar 

  9. Koga, N. & Morokuma, K. J. Am. chem. Soc. 115, 6883–6892 (1993).

    Article  CAS  Google Scholar 

  10. Fritz, V. G., Habel, D., Kummer, D. & Teichmann, G. Z. anorg. allg. Chem. 302, 60–80 (1959).

    Article  CAS  Google Scholar 

  11. Schubert, U. Adv. organomet. Chem. 30, 151–187 (1990).

    Article  CAS  Google Scholar 

  12. Aizenberg, M. & Milstein, D. Angew. Chem. int. Edn engl. 33, 317–319 (1994).

    Article  Google Scholar 

  13. Tilley, T. D. in The Silicon-Heteroatom Bond (eds Patai, S. & Rappoport, Z.) 288–359 (Wiley, New York, 1991).

    Google Scholar 

  14. McMillen, D. F. & Golden, D. M. A. Rev. phys. Chem. 33, 493–532 (1982).

    Article  CAS  ADS  Google Scholar 

  15. Walsh, R. in The Chemistry of Organic Silicon Compounds (eds Patai, S. & Rappoport, Z.) 371–392 (Wiley, New York, 1989).

    Book  Google Scholar 

  16. Sinflet, J. H. in Catalysis: Science and Technology Vol. 1 (eds Anderson, J. R. & Boudart, M.) 257–300 (Springer, New York, 1981).

    Google Scholar 

  17. Field, L. D. in Selective Hydrocarbon Activation (eds Davies, J. A., Watson, P. L., Liebman, J. F. & Greenberg, A.) 241–264 (VCH, New York, 1990).

    Google Scholar 

  18. Griffin, G. W. Angew. Chem. int. Edn engl. 10, 537–547 (1971).

    Article  Google Scholar 

  19. Watson, P. L. & Roe, D. C. J. Am. chem. Soc. 104, 6471–6473 (1982).

    Article  CAS  Google Scholar 

  20. Bunel, E., Burger, B. J. & Bercaw, J. E. J. chem. Soc. 110, 976–978 (1988).

    Article  CAS  Google Scholar 

  21. Yang, X., Jia, L. & Marks, T. J. J. Am. chem. Soc. 115, 3392–3394 (1993).

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

Authors

Rights and permissions

Reprints and permissions

About this article

Cite this article

Gozin, M., Aizenberg, M., Liou, SY. et al. Transfer of methylene groups promoted by metal complexation. Nature 370, 42–44 (1994). https://doi.org/10.1038/370042a0

Download citation

  • Received:

  • Accepted:

  • Issue Date:

  • DOI: https://doi.org/10.1038/370042a0

  • Springer Nature Limited

This article is cited by

Navigation