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

Xiao-Fang Liu; Xiao-Ya Li; Chang Qiao; Liang-Nian He

doi:10.1055/s-0036-1591533

Synlett, Table of Contents

Synlett 2018; 29(05): 548-555
DOI: 10.1055/s-0036-1591533

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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

,

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

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Abstract

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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

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References

References

1a Liu Q. Wu LP. Jackstell R. Beller M. Nat. Commun. 2015; 6: 5933
1b Zhang Z. Ju T. Ye J.-H. Yu D.-G. Synlett 2017; 28: 741
1c Song Q.-W. Zhou Z.-H. He L.-N. Green Chem. 2017; 19: 3707

2 Mikkelsen M. Jørgensen M. Krebs FC. Energy Environ. Sci. 2010; 3: 43
3 Lescot C. Nielsen DU. Makarov IS. Lindhardt AT. Daasbjerg K. Skrydstrup T. J. Am. Chem. Soc. 2014; 136: 6142
4 Li Y.-N. He L.-N. Liu A.-H. Lang X.-D. Yang Z.-Z. Yu B. Luan C.-R. Green Chem. 2013; 15: 2825
5 Li Y.-N. Ma R. He L.-N. Diao Z.-F. Catal. Sci. Technol. 2014; 4: 1498
6 Heim LE. Konnerth H. Prechtl MH. G. Green Chem. 2017; 19: 2347
7 Park S. Bézier D. Brookhart M. J. Am. Chem. Soc. 2012; 134: 11404
8 Das Neves Gomes C. Jacquet O. Villiers C. Thuéry P. Ephritikhine M. Cantat T. Angew. Chem. Int. Ed. 2012; 51: 187

Recent reviews on reductive functionalization of CO₂:

9a Tlili A. Blondiaux E. Frogneux X. Cantat T. Green Chem. 2015; 17: 157
9b Klankermayer J. Wesselbaum S. Beydoun K. Leitner W. Angew. Chem. Int. Ed. 2016; 55: 7296
9c Li Y. Cui X. Dong K. Junge K. Beller M. ACS Catal. 2017; 7: 1077

10a Kobayashi K. Nagato S. Kawakita M. Morikawa O. Konishi H. Chem. Lett. 1995; 24: 575
10b Jackson A. Meth-Cohn O. J. Chem. Soc., Chem. Commun. 1995; 1319

11 Gerack C. McElwee-White L. Molecules 2014; 19: 7689
12 Krocher OA. Koppel R. Baiker A. Chem. Commun. 1997; 453
13 Zhang L. Han Z. Zhao X. Wang Z. Ding K. Angew. Chem. Int. Ed. 2015; 54: 6186
14 Liu H. Mei Q. Xu Q. Song J. Liu H. Han B. Green Chem. 2017; 19: 196
15 Daw P. Chakraborty S. Leitus G. Diskin-Posner Y. Ben-David Y. Milstein D. ACS Catal. 2017; 7: 2500
16 Dong K. Razzaq R. Hu Y. Ding K. Top. Curr. Chem. 2017; 375: 23

Selected examples for transition-metal-catalyzed N-formylation:

17a Luo R. Lin X. Chen Y. Zhang W. Zhou X. Ji H. ChemSusChem 2017; 10: 1224
17b Motokura K. Takahashi N. Kashiwame D. Yamaguchi S. Miyaji A. Baba T. Catal. Sci. Technol. 2013; 3: 2392
17c Nguyen TV. Q. Yoo W.-J. Kobayashi S. Angew. Chem. Int. Ed. 2015; 54: 9209

18 Bhanage B. Nale D. Synlett 2016; 27: 1413
19 Jacquet O. Das Neves Gomes C. Ephritikhine M. Cantat T. J. Am. Chem. Soc. 2012; 134: 2934
20 Saptal VB. Bhanage BM. ChemSusChem 2016; 9: 1980
21 Chong CC. Kinjo R. Angew. Chem. Int. Ed. 2015; 54: 12116
22 Riduan SN. Ying JY. Zhang Y. J. Catal. 2016; 343: 46
23 Hao L. Zhao Y. Yu B. Yang Z. Zhang H. Han B. Gao X. Liu Z. ACS Catal. 2015; 5: 4989
24 Ke ZG. Hao LD. Gao X. Zhang HY. Zhao YF. Yu B. Yang ZZ. Chen Y. Liu ZM. Chem. Eur. J. 2017; 23: 9721
25 Lv H. Xing Q. Yue C. Lei Z. Li F. Chem. Commun. 2016; 52: 6545
26 Song J. Zhou B. Liu H. Xie C. Meng Q. Zhang Z. Han B. Green Chem. 2016; 18: 3956
27 Zhao T.-X. Zhai G.-W. Liang J. Li P. Hu X.-B. Wu Y.-T. Chem. Commun. 2017; 53: 8046
28 Hao L. Zhang H. Luo X. Wu C. Zhao Y. Liu X. Gao X. Chen Y. Liu Z. J. CO2 Util. 2017; 22: 208
29 Vessally E. Didehban K. Babazadeh M. Hosseinian A. Edjlali L. J. CO2 Util. 2017; 21: 480
30 Jacquet O. Das Neves Gomes C. Ephritikhine M. Cantat T. ChemCatChem 2013; 5: 117
31 Gao X. Yu B. Yang ZZ. Zhao YF. Zhang HG. Hao LD. Han BX. Liu ZM. ACS Catal. 2015; 5: 6648
32 Zhang ZB. Sun QS. Xia CG. Sun W. Org. Lett. 2016; 18: 6316

33a Schönherr H. Cernak T. Angew. Chem. Int. Ed. 2013; 52: 12256
33b Meyer KD. Saletore Y. Zumbo P. Elemento O. Mason CE. Jaffrey SR. Cell 2012; 149: 1635

34 Tundo P. Selva M. Acc. Chem. Res. 2002; 35: 706
35 Jacquet O. Frogneux X. Das Neves Gomes C. Cantat T. Chem. Sci. 2013; 4: 2127

Ru-catalyzed N-methylation with CO₂ and H₂:

36a Li Y. Fang X. Junge K. Beller M. Angew. Chem. Int. Ed. 2013; 52: 9568
36b Li Y. Sorribes I. Yan T. Junge K. Beller M. Angew. Chem. Int. Ed. 2013; 52: 12156
36c Beydoun K. vom Stein T. Klankermayer J. Leitner W. Angew. Chem. Int. Ed. 2013; 52: 9554

37 González-Sebastián L. Flores-Alamo M. García JJ. Organometallics 2015; 34: 763
38 Santoro O. Lazreg F. Minenkov Y. Cavallo L. Cazin CS. J. Dalton Trans. 2015; 44: 18138
39 Cui X. Dai X. Zhang Y. Deng Y. Shi F. Chem. Sci. 2014; 5: 649

Selected examples for N-methylation with formic acid as C₁ source:

40a Sorribes I. Junge K. Beller M. Chem. Eur. J. 2014; 20: 7878
40b Qiao C. Liu X.-F. Liu X. He L.-N. Org. Lett. 2017; 19: 1490
40c Fu M.-C. Shang R. Cheng W.-M. Fu Y. Angew. Chem. Int. Ed. 2015; 54: 9042

41 Blondiaux E. Pouessel J. Cantat T. Angew. Chem. Int. Ed. 2014; 53: 12186
42 Das S. Bobbink FD. Laurenczy G. Dyson PJ. Angew. Chem. Int. Ed. 2014; 53: 12876
43 Chen WC. Shen JS. Jurca T. Peng CJ. Lin YH. Wang YP. Shih WC. Yap GP. Ong TG. Angew. Chem. Int. Ed. 2015; 54: 15207
44 Yang Z. Yu B. Zhang H. Zhao Y. Ji G. Ma Z. Gao X. Liu Z. Green Chem. 2015; 17: 4189
45 Niu H. Lu L. Shi R. Chiang C.-W. Lei A. Chem. Commun. 2017; 53: 1148
46 Liu X.-F. Qiao C. Li X.-Y. He L.-N. Green Chem. 2017; 19: 1726
47 Goeppert A. Czaun M. Jones J.-P. Surya Prakash GK. Olah GA. Chem. Soc. Rev. 2014; 43: 7995

Ru- and Co-based catalytic protocol for the synthesis of dimethoxymethane with CO₂ as –CH₂– source:

48a Schieweck BG. Klankermayer J. Angew. Chem. Int. Ed. 2017; 56: 10854
48b Thenert K. Beydoun K. Wiesenthal J. Leitner W. Klankermayer J. Angew. Chem. Int. Ed. 2016; 55: 12266

49 Frogneux X. Blondiaux E. Thuéry P. Cantat T. ACS Catal. 2015; 5: 3983
50 Jin G. Werncke CG. Escudié Y. Sabo-Etienne S. Bontemps S. J. Am. Chem. Soc. 2015; 137: 9563
51 Zhu D.-Y. Fang L. Han H. Wang Y. Xia J.-B. Org. Lett. 2017; 19: 4259
52 Das S. Bobbink FD. Bulut S. Soudani M. Dyson PJ. Chem. Commun. 2016; 52: 2497
53 Zhou H. Wang G.-X. Zhang W.-Z. Lu X.-B. ACS Catal. 2015; 5: 6773

54a Liu X.-F. Ma R. Qiao C. Cao H. He L.-N. Chem. Eur. J. 2016; 22: 16489

A similar fluoride-catalyzed N-formylation protocol was reported almost simultaneously:

54b Hulla M. Bobbink FD. Das S. Dyson PJ. ChemCatChem 2016; 8: 3338

55 Fang C. Lu C. Liu M. Zhu Y. Fu Y. Lin B.-L. ACS Catal. 2016; 6: 7876
56 Liu XF. Li XY. Qiao C. Fu HC. He LN. Angew. Chem. Int. Ed. 2017; 56: 7425

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

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