Citation: Zou Hongyan, Wang Zhong-Liang, Cao Yang, Huang Genping. Mechanism of rhodium(Ⅲ)-catalyzed formal C(sp³)-H activation/spiroannulation of α-arylidene pyrazolones with alkynes:A computational study[J]. Chinese Chemical Letters, ;2018, 29(9): 1355-1358. doi: 10.1016/j.cclet.2017.10.034 shu

Mechanism of rhodium(Ⅲ)-catalyzed formal C(sp³)-H activation/spiroannulation of α-arylidene pyrazolones with alkynes:A computational study

a.
Tianjin Key Laboratory of Water Resources and Environment, Tianjin Normal University, Tianjin 300387, China
b.
Department of Chemistry, School of Science, Tianjin University, Tianjin 300072, China
c.
Institute of New Energy, Shenzhen 518031, China

Corresponding author: Wang Zhong-Liang, wangzhongliang@vip.skleg.cn Huang Genping, gphuang@tju.edu.cn
Received Date: 15 September 2017
Revised Date: 15 October 2017
Accepted Date: 26 October 2017
Available Online: 27 September 2017

Figures(4)

The rhodium-catalyzed formal C(sp³)-H activation/spiroannulation of α-arylidene pyrazolones with alkynes was investigated by means of density functional theory calculations. The calculations indicate that the spiroannulation through the proposed C-C reductive elimination is kinetically unfeasible. Instead, the C-C coupling from the eight-membered rhodacycle was proposed to account for the experimental results. The overall catalytic cycle consists of six steps:(1) the keto-enol isomerization; (2) the O-H deprotonation, (3) the C(sp²)-H bond cleavage; (4) the migratory insertion of alkyne into the Rh-C bond; (5) the C-C coupling and (6) the regeneration of the active catalyst.
- Rhodium,
- Spiroannulation,
- C-H activation,
- Reaction mechanism,
- DFT calculations
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Mechanism of rhodium(Ⅲ)-catalyzed formal C(sp3)-H activation/spiroannulation of α-arylidene pyrazolones with alkynes:A computational study

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通讯作者: 陈斌, bchen63@163.com

Mechanism of rhodium(Ⅲ)-catalyzed formal C(sp³)-H activation/spiroannulation of α-arylidene pyrazolones with alkynes:A computational study