A theoretical study on platinum-catalyzed cycloisomerization of 2-ethynyl-1-ferrocenylbenzene

作者：Zhang, XingHui^*; Jiang, LiPing; Li, ShanShan; Wang, KeTai

来源：Computational and Theoretical Chemistry, 2017, 1115: 56-62.

DOI：10.1016/j.comptc.2017.05.005

• Platinum-catalyzed
• Cycloisomerization
• Ferrocene derivatives
• Naphthalene fused ferrocene

Density functional theory calculations are carried out to explore the reaction mechanism for the cycloisomerization of 2-ethynyl-1-ferrocenylbenzene by using PtCl2 as a catalyst at the M06-2X/6-31G (d, p) (LanL2DZ (f) for Pt, Fe) level. The calculation results prove that the platinum-catalyzed cycloisomerization of 2-ethynyl-1-ferrocenylbenzene includes two possible pathways and three steps to afford naphthalene fused ferrocene. One reaction pathway is based on the 6-endo-dig cyclization mechanism, and another pathway is on the alkyne-vinylidene rearrangement mechanism. The channel I has a lower activation free energy by 17.0 kcal/mol, which is more favorable to obtain the major product 2a. However, the activation barrier for the channel 2 is relatively high by 22.7 kcal/mol. Through the detailed computational study, the results show that the platinum-catalyzed cycloisomerization has the good reactivity and high yield, giving a good explanation for the experimental observed major product.

• 出版日期2017-9-1
• 单位兰州大学