Skip to main content
Log in

Manganese-Catalyzed Carbomagnesation of Alkynes

  • Published:
Catalysis Surveys from Asia Aims and scope Submit manuscript

Abstract

The development of manganese-catalyzed carbomagnesation of alkynes is reviewed. Manganese salts mediate the efficient addition of a variety of Grignard reagents to alkynes. Allyl, aryl, and alkyl Grignard reagents participate in these reactions. In many cases, a hetero atom such as oxygen or nitrogen in substrates facilitates the addition reaction. Stoichiometric carbometalation reactions with manganese ate complexes are also discussed, as is cyclization of 1,6-diynes and 1,6-enynes via carbometalation with triallylmanganate.

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. R.C. Larock, Comprehensive Organic Transformations (VCH, New York, 1989) p. 105; Preparation of Alkenes, ed. J.M.J. Williams (Oxford University Press, New York, 1996).

    Google Scholar 

  2. P. Knochel, in: Comprehensive Organic Synthesis, Vol. 4, eds. B.M. Trost and I. Fleming (Pergamon Press, Oxford, 1991) p. 865; W. Oppolzer, in: Comprehensive Organic Synthesis, Vol. 5, eds. B.M. Trost and I. Fleming (Pergamon Press, Oxford, 1991) p. 29.

    Google Scholar 

  3. J. Hibino, S. Nakatsukasa, K. Fugami, S. Matsubara, K. Oshima and H. Nozaki, J. Am. Chem. Soc. 107 (1985) 6416; K. Fugami, S. Nakatsukasa, K. Oshima, K. Utimoto and H. Nozaki, Chem. Lett. (1986) 869; K. Fugami, J. Hibino, S. Nakatsukasa, S. Matsubara, K. Oshima, K. Utimoto and H. Nozaki, Tetrahedron 44 (1988) 4277.

  4. J.F. Normant and A. Alexakis, Synthesis (1981) 841; F.W. von Rein and H.G. Richey, Jr., Tetrahedron Lett. (1971) 3777.

  5. B. Jousseaume and J.-G. Duboudin, J. Organomet. Chem. 91 (1975) Cl. Conjugate addition of the allylic copper species has been reported: B.H. Lipshutz and C. Hackmann, J. Org. Chem. 59 (1994) 7437.

  6. K. Okada, K. Oshima and K. Utimoto, J. Am. Chem. Soc. 118 (1996) 6076; J. Tang, K. Okada, H. Shinokubo and K. Oshima, Tetrahedron 53 (1997) 5061.

  7. We have no evidence regarding the structure of these reagents and use these formulae tentatively. Three different types of organomanganese reagents (RMnX, R2Mn;R3Mn_Mtl+) have been reported: J.F. Normant and G. Cahiez, in: Modern Synthetic Methods, Vol. 3, ed. R. Scheffold (Otto Salle Verlag, Frankfurt am Main, 1983). The syntheses and X-ray crystal structures of [Li(tmed)]2[MnMe4] and [Li(tmed)]2[MnEt4] have been reported: R.J. Morris and G.S. Girolami, Organometallics 8 (1989) 1478. The reaction of tetrafurylmanganate has been reported: G. Cahiez, P.-Y. Chavant and E. Metais, Tetrahedron Lett. 33 (1992) 5245.

    Google Scholar 

  8. For examples of phenylalumination of acetylenes, see J.J. Eisch and W.C. Kaska, J. Am. Chem. Soc. 88 (1966) 2976; J.J. Eisch, R. Amtmann and M.W. Foxton, J. Organomet. Chem. 16 (1969) P55; J.J. Eisch and R. Amtmann, J. Org. Chem. 37 (1972) 3410. Diarylation with aryltributylstannane: H. Oda, M. Morishita, K. Fugami, H. Sano and M. Kosugi, Chem. Lett. (1996) 811. Ni-catalyzed phenylzincation: T. Stu¨ demann and P. Knochel, Angew. Chem., Int. Ed. Engl. 36 (1997) 93.

  9. H. Yorimitsu, J. Tang, K. Okada, H. Shinokubo and K. Oshima, Chem. Lett. (1998) 11.

  10. S. Nishimae, R. Inoue, H. Shinokubo and K. Oshima, Chem. Lett. (1998) 785.

  11. For silylmetalation of alkynes, see H. Hayami, M. Sato, S. Kanemoto, Y. Morizawa, K. Oshima and H. Nozaki, J. Am. Chem. Soc. 105 (1983) 4491; K. Nozaki, K. Wakamatsu, T. Nonaka, W. Tückmantel, K. Oshima and K. Utimoto, Tetrahedron Lett. 27 (1986) 2007; K. Wakamatsu, T. Nonaka, Y. Okuda, W. Tückmantel, K. Oshima, K. Utimoto and H. Nozaki, Tetrahedron 42 (1986) 4427; I. Fleming, T.W. Newton and F. Roessler, J. Chem. Soc. Perkin Trans. I (1981) 2527; K. Tamao, M. Akita, R. Kanatani, N. Ishida and M. Kumada, J. Organomet. Chem. 226 (1982) C9.

  12. J. Tang, H. Shinokubo and K. Oshima, Bull. Chem. Soc. Jpn. 70 (1997) 245.

    Google Scholar 

  13. J. Tang, H. Shinokubo and K. Oshima, Organometallics 17 (1998) 290.

    Google Scholar 

  14. Recently, we have reported selective formation of six-membered bicyclic compounds with chromium reagents: T. Nishikawa, H. Kakiya, H. Shinokubo and K. Oshima, J. Am. Chem. Soc. 123 (2001) 4629.

Download references

Author information

Authors and Affiliations

Authors

Rights and permissions

Reprints and permissions

About this article

Cite this article

Shinokubo, H., Oshima, K. Manganese-Catalyzed Carbomagnesation of Alkynes. Catalysis Surveys from Asia 7, 39–46 (2003). https://doi.org/10.1023/A:1023432624548

Download citation

  • Issue Date:

  • DOI: https://doi.org/10.1023/A:1023432624548

Navigation