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.
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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