Mechanistic Study on Gold-Catalyzed Highly Selective Hydroamination of Alkylidenecyclopropanes

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• 作者：Chen Wang ; Xiao-Rong Ren ; Chen-Ze Qi ; Hai-Zhu Yu
• 刊名：Journal of Organic Chemistry
• 出版年：2016
• 出版时间：September 2, 2016
• 年：2016
• 卷：81
• 期：17
• 页码：7326-7335
• 全文大小：662K
• 年卷期：0
• ISSN：1520-6904

文摘

Density functional theory calculations have been carried out to study the mechanism of the gold-catalyzed highly selective hydroamination of alkylidenecyclopropanes. Two main mechanisms (i.e., double-bond activation-first and three-membered-ring activation-first mechanisms) have been examined. The double-bond activation-first mechanism results in the alkene hydroamination product, and it mainly consists of three steps: C–N bond formation, C–C bond rotation, and protodeauration (rate-determining step). Meanwhile, the three-membered-ring activation-first mechanism finally produces allylic amines, and it occurs via the ring-opening (rate-determining step), C–N bond formation, and protodeauration steps. The calculation results show good agreement with the experimental outcomes on the chemo-, regio-, and diastereoselectivity. On this basis, we found that the regioselectivity is caused by the C–C bond rotation step, while the diastereoselectivity is determined by both the C–C bond rotation and the protodeauration steps in the double-bond activation-first mechanism.