Citation: Rongchang Luo, Xiaowei Lin, Jing Lu, Xiantai Zhou, Hongbing Ji. Zinc phthalocyanine as an efficient catalyst for halogen-free synthesis of formamides from amines via carbon dioxide hydrosilylation under mild conditions[J]. Chinese Journal of Catalysis, ;2017, 38(8): 1382-1389. shu

Zinc phthalocyanine as an efficient catalyst for halogen-free synthesis of formamides from amines via carbon dioxide hydrosilylation under mild conditions

a School of Chemistry, Key Laboratory of Low-Carbon Chemistry & Energy Conservation of Guangdong Province, Sun Yat-sen University, Guangzhou 510275, Guangdong, China;
b Liede Experimental School of Guangzhou Tianhe High School, Guangzhou 510623, Guangdong, China;
c School of Chemical Engineering and Technology, Sun Yat-sen University, Zhuhai 519000, Guangdong, China

Received Date: 12 May 2017
Revised Date: 18 June 2017

Fund Project: This work was supported by the National Natural Science Foundation of China (21676306, 21425627), the National Key Research and Development Program of China (2016YFA0602900), the Natural Science Foundation of Guangdong Province (2016A030310211), and the Characteristic Innovation Project (Natural Science) of Guangdong Colleges and Universities.

The combination of a zinc phthalocyanine (ZnPc) catalyst and a stoichiometric amount of dimethyl formamide (DMF) provided a simple route to formamide derivatives from amines, CO₂, and hydrosilanes under mild conditions. We deduced that formation of an active zinc-hydrogen (Zn-H) species promoted hydride transfer from the hydrosilane to CO₂. The cooperative activation of the Lewis acidic ZnPc by strongly polar DMF, led to formation of activated amines and hydrosilanes, which promoted the chemical reduction of CO₂. Consequently, the binary ZnPc/DMF catalytic system showed excellent yields and superior chemoselectivity, representing a simple and sustainable pathway for the reductive transformation of CO₂ into valuable chemicals as an alternative to conventional halogen-containing process.
- Carbon dioxide,
- Zinc phthalocyanine,
- Cooperative effect,
- N-formylation,
- Hydrosilanes
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