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Synlett 2018; 29(05): 548-555
DOI: 10.1055/s-0036-1591533
DOI: 10.1055/s-0036-1591533
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Transition-Metal-Free Catalysis for the Reductive Functionalization of CO2 with Amines
This 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)
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
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Recent reviews on reductive functionalization of CO2:
Selected examples for transition-metal-catalyzed N-formylation:
Ru-catalyzed N-methylation with CO2 and H2:
Selected examples for N-methylation with formic acid as C1 source:
Ru- and Co-based catalytic protocol for the synthesis of dimethoxymethane with CO2 as –CH2– source:
A similar fluoride-catalyzed N-formylation protocol was reported almost simultaneously: