Citation: Wang Yaqi, Yin Qiang, Guo Dun, Han Limin, Sun Qi, Hong Hailong, Suo Quanling. Carbonyl Cobalt-Catalyzed Cyclotrimerization of Terminal Alkynes in Supercritical Carbon Dioxide[J]. Chinese Journal of Organic Chemistry, ;2019, 39(10): 2898-2905. doi: 10.6023/cjoc201904021 shu

Carbonyl Cobalt-Catalyzed Cyclotrimerization of Terminal Alkynes in Supercritical Carbon Dioxide

Chemical Engineering College, Inner Mongolia University of Technology, Hohhot 010051

Corresponding author: Suo Quanling, szj@imut.edu.cn
Received Date: 9 April 2019
Revised Date: 14 May 2019
Available Online: 28 October 2019
Fund Project: Project supported by the National Natural Science Foundation of China (No. 21266019) and the Natural Science Foundation of Inner Mongolia Autonomous Region of China (No. 2015MS0204)the Natural Science Foundation of Inner Mongolia Autonomous Region of China 2015MS0204the National Natural Science Foundation of China 21266019

Figures(1)

Atom-efficient [2+2+2] cycloaddition reaction of alkynes in green solvent supercritical carbon dioxide (ScCO₂) is an environmentally friendly reaction process that conforms to the principles of green chemistry. Cyclotrimerization of terminal alkynes catalyzed by Co₂(CO)₈ in pure ScCO₂ has been studied to obtain 1, 2, 4-trisubstituted benzene derivatives with excellent selectivity. The reaction conditions for the cyclotrimerization were optimized, such as concentration of catalyst, CO₂ pressure, reaction temperature and time. The solubility and phase behavior of the reaction materials and catalysts in ScCO₂ medium were discussed, and the mechanism of Co₂(CO)₈ catalyzed cyclotrimerization of terminal alkynes was assumed. The reaction substrate was extended from C≡C (alkyne) to C≡N (nitrile), and the alkyne-nitrile cycloaddition reaction in ScCO₂ was preliminary explored. Our optimized catalytic system for the cyclotrimerization of terminal alkynes exhibited wide substrate scope and high product selectivity, in which no organic co-solvent or additives were added. It provided a green synthetic method for 1, 2, 4-trisubstituted benzenes.
- supercritical carbon dioxide,
- terminal alkyne,
- cyclotrimerization reaction,
- carbonyl cobalt catalyst,
- alkyne-nitrile cycloaddition reaction
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