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Synlett 2018; 29(05): 548-555
DOI: 10.1055/s-0036-1591533
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© Georg Thieme Verlag Stuttgart · New York

Transition-Metal-Free Catalysis for the Reductive ­Functionalization of CO2 with Amines

Xiao-Fang Liu
State Key Laboratory and Institute of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, College of Chemistry, Nankai University, 4 Weijin Rd., Tionjin 300071, P. R. of China   Email: heln@nankai.edu.cn
,
Xiao-Ya Li
State Key Laboratory and Institute of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, College of Chemistry, Nankai University, 4 Weijin Rd., Tionjin 300071, P. R. of China   Email: heln@nankai.edu.cn
,
Chang Qiao
State Key Laboratory and Institute of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, College of Chemistry, Nankai University, 4 Weijin Rd., Tionjin 300071, P. R. of China   Email: heln@nankai.edu.cn
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Liang-Nian He  *
State Key Laboratory and Institute of Elemento-Organic Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, College of Chemistry, Nankai University, 4 Weijin Rd., Tionjin 300071, P. R. of China   Email: heln@nankai.edu.cn
› Author AffiliationsThis work was financially supported by National Key Research and Development Program (2016YFA0602900), National Natural Science Foundation of China (21472103, 21421001, 21421062), the Natural Science Foundation of Tianjin (16JCZDJC39900), and the Ph.D. ­Candidate Research Innovation Fund of the College of Chemistry ­Nankai University (020-96172407).
Further Information

Publication History

Received: 06 December 2017

Accepted after revision: 27 December 2017

Publication Date:
31 January 2018 (online)

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Abstract

Reductive functionalization of CO2 with amines and a reductant, which combines both reduction of CO2 and C–N bond formation in one pot to produce versatile chemicals and energy-storage materials such as formamides, aminals, and methylamines that are usually derived from petroleum feedstock, would be appealing and promising. Herein, we give a brief review on recent developments in the titled CO2 chemistry by employing transition-metal-free catalysis, which can be catalogued as below according to the diversified energy content of the products, that is formamides, aminals, and methylamines being consistent with 2-, 4-, and 6-electron reduction of CO2, respectively. Notably, hierarchical reduction of CO2 with amines to afford at least two products, for example, formamides and methylamines, could be realized with the same catalyst through tuning the hydrosilane type, reaction temperature, or CO2 pressure. Finally, the opportunities and challenges of the reductive functionalization of CO2 with amines are also highlighted.

1 Introduction

2 2-Electron Reduction of CO2 to Formamide

3 6-Electron Reduction of CO2 to Methylamine

4 4-Electron Reduction of CO2 to Aminal

5 Hierarchical Reduction of CO2 with Amines

6 Conclusion

Key words

carbon dioxide - hierarchical reduction - transition-metal-free catalyst - formamide - methylamine - aminals - synthetic methods