Springer Nature is making SARS-CoV-2 and COVID-19 research free. View research | View latest news | Sign up for updates

Mechanism of skeletal reorganization of 1,6-enynes catalyzed by GaCl3

  • 15 Accesses

  • 3 Citations


The mechanism of skeletal reorganization of 1,6-enynes catalyzed by GaCl3 has been studied with the density functional method at the B3LYP/6-31G* level. The structures and energies of the stationary points were calculated to identify the activation barriers. The transition states were testified with vibration analysis and IRC calculations. The results of calculation show that the conversion of 1,6-enynes is a step-wise reaction. The whole reaction process is formation and migration of three-membered cycle involving a three-center and two-electron (3c-2e) bond. High stereoselectivity of the reaction is in good agreement with experimental results.

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


  1. 1.

    Aubert, C., Buisine O., Malacria M., The behavior of 1, n-enynes in the presence of transition metals, Chem. Rev., 2002, 102: 813–834.

  2. 2.

    Trost, B. M., Palladium-catalyzed cycloisomerizations of enynes and related reactions, Acc. Chem. Res., 1990, 23: 34–42.

  3. 3.

    Trost B. M., Tanoury, G. J., An unusual mechanism of a palladiumcatalyzed intermolecular carbametalaton. A novel palladium-catalyzed rearrangement, J. Am. Chem. Soc., 1988, 110: 1636–1638.

  4. 4.

    Trost, B. M., Trost, M. K., Mechanistic dichotomies in Pd catalyzed enyne metathesis of cyclic olefins, J. Am. Chem. Soc., 1991, 113: 3647–3650.

  5. 5.

    Chatani, N., Morimoto, T., Muto, T. et al., Highly selective skeletal reorganization of 1,6- and 1,7-enynes to 1-vinylcycloalkenes catalyzed by [RuCl2 (CO)3]2, J. Am. Chem. Soc., 1994, 116: 6049–6050.

  6. 6.

    Chatani, N., Furukawa, N., Sakurai, H. et al., PtCl2-catalyzed conversion of 1,6- and 1,7-enynes to 1-vinylcycloalkenes. Anomalous bond connection in skeletal reorganization of enynes, Organometallics, 1996, 15: 901–903.

  7. 7.

    Chatani, N., Inoue, H., Kotsuma, T. et al., Skeletal reorganization of enynes to 1-vinylcycloalkenes catalyzed by GaCl3, J. Am. Chem. Soc., 2002, 12: 10294–10295.

  8. 8.

    Méndez, M., Munz, M. P., Nevado, C. et al., Cyclizations of enynes catalyzed by PtCl3 or other transition metal chlorides: divergent reaction pathways, J. Am. Chem. Soc., 2001, 123: 10511–10520.

  9. 9.

    Reed, A. E., Weinstock, R. B., Weinhold, F. J., Natural population analysis, J. Chem. Phys., 1985, 83: 735–746.

  10. 10.

    Reed, A. E., Curtiss, L. A., Weinhold F., Intermolecular interactions from a natural bond orbital, donor-acceptor viewpoint, Chem. Rev., 1988, 88: 899–926.

Download references

Author information

Correspondence to Daiqian Xie.

About this article

Cite this article

Xu, K., Wu, Y., Xie, D. et al. Mechanism of skeletal reorganization of 1,6-enynes catalyzed by GaCl3 . Chin. Sci. Bull. 49, 883–885 (2004). https://doi.org/10.1007/BF03184003

Download citation


  • 1,6-enyne
  • GaCl3
  • B3LYP