Catalytic Synthesis of Formamides with Carbon Dioxide and Amines

Citation: ZHANG Yujing, DAI Xingchao, WANG Hongli, SHI Feng. Catalytic Synthesis of Formamides with Carbon Dioxide and Amines[J]. Acta Physico-Chimica Sinica, 2018, 34(8): 845-857. doi: 10.3866/PKU.WHXB201701081 shu

二氧化碳和胺催化合成甲酰胺反应研究

张玉景 ^1,2, ,
代兴超 ^1,2, ,
王红利 ^1, ,
石峰 ^{1,
,}

1.
中国科学院兰州化学物理研究所，兰州 730000
2.
中国科学院大学，北京 100049

作者简介:

SHI Feng completed his Ph.D. studies in catalysis at LICP, CAS in 2004. After a three-year postdoctoral research in LIKAT in Germany, he joined the faculty of LICP in 2008 as Hundred Talents Program of CAS. Since 2016 SHI Feng is the deputy director of the State Key Laboratory for Oxo Synthesis and Selective Oxidation. His research focuses on nano-catalysis in fine chemical synthesis and C₁ chemistry;

通讯作者: 石峰, fshi@licp.cas.cn

基金项目:
国家自然科学基金 91745106

国家自然科学基金 21633013

国家自然科学基金(21633013, 91745106)与国家重大研究与发展项目(2017YFA0403103)资助项目

国家重大研究与发展项目 2017YFA0403103

摘要: 二氧化碳是碳资源利用的最终形式，也是一种绿色的碳一资源。通过催化化学的方法将二氧化碳转化为高附加值精细化学品是二氧化碳循环利用的有效途径。酰胺类化合物是一类重要的化工原料和溶剂，广泛应用于医药、农药、日用化学品及石油化工等众多领域且需求量巨大。因此，以二氧化碳为羰源，通过高效催化体系的建立实现二氧化碳与胺反应合成甲酰胺具有重要意义。本文分别从催化体系、还原剂和反应机理等角度综述了这一领域近年来的主要研究成果。其中，催化体系可分为贵金属催化剂如Ir、Pd、Pt、Ru、Rh，非贵金属催化剂如Ni、Mo、Cu、Fe、Co、Zn、Al，有机分子催化剂和无催化剂体系，常用的还原剂为H₂，硅烷和硼烷。在此基础上，对不同催化体系的典型反应机理进行了讨论。

关键词:

二氧化碳
/ 胺
/ 甲酰胺
/ 羰基化

English

Catalytic Synthesis of Formamides with Carbon Dioxide and Amines

1.
State Key Laboratory for Oxo Synthesis and Selective Oxidation, Center for Green Chemistry and Catalysis, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000, P. R. China
2.
University of Chinese Academy of Sciences, Beijing 100049, P. R. China

Author Bio: SHI Feng completed his Ph.D. studies in catalysis at LICP, CAS in 2004. After a three-year postdoctoral research in LIKAT in Germany, he joined the faculty of LICP in 2008 as Hundred Talents Program of CAS. Since 2016 SHI Feng is the deputy director of the State Key Laboratory for Oxo Synthesis and Selective Oxidation. His research focuses on nano-catalysis in fine chemical synthesis and C₁ chemistry;

Corresponding author: SHI Feng, fshi@licp.cas.cn

Received Date: 30 November 2017
Accepted Date: 29 December 2017
Revised Date: 29 December 2017
Available Online: 15 August 2018
Fund Project:

The project was supported by the National Natural Science Foundation of China (21633013, 91745106) and National Key Research and Development Program of China (2017YFA0403103)

Abstract: Carbon dioxide is a green C₁ resource that can be efficiently recycled by catalytic transformation into value-added chemicals. Formamides are important intermediates and solvents that are used extensively in pharmaceutical, daily-chemical, and petrochemical industry. Therefore, it is worthwhile to synthesize formamides with CO₂ and amines. In this review, the main advancements in the synthesis of formamides by using CO₂ as the C₁ feedstock with noble metal catalysts (Ir, Pd, Pt, Ru, Rh, etc.), non-noble metal catalysts (Ni, Mo, Cu, Fe, Co, Zn, Al, etc.), organocatalysts, and catalyst-free systems have been summarized. In addition, the role of the reducing agents such as H₂, silanes, and boranes involved in these transformations has also been reviewed. In addition, the reaction mechanisms with the different catalyst systems have been discussed.

Key words:

1. [1]
  Aresta, M.; Dibenedetto, A. Dalton Trans. 2007, 2975. doi: 10.1039/B700658F
2. [2]
  Mikkelsen, M.; J rgensen, M.; Krebs, F. C. Energ. Environ. Sci. 2010, 3, 43. doi: 10.1039/B912904A
3. [3]
  Huang, K.; Sun, C.-L.; Shi, Z.-J. Chem. Soc. Rev. 2011, 40, 2435. doi: 10.1039/C0CS00129E
4. [4]
  Qiao, J.; Liu, Y.; Hong, F.; Zhang, J. Chem. Soc. Rev. 2014, 43, 631. doi: 10.1039/C3CS60323G
5. [5]
  Riduan, S. N.; Zhang, Y. Dalton Trans. 2010, 39, 3347. doi: 10.1039/B920163G
6. [6]
  Wang, W.; Wang, S.; Ma, X.; Gong, J. Chem. Soc. Rev. 2011, 40, 3703. doi: 10.1039/C1CS15008A
7. [7]
  Thenert, K.; Beydoun, K.; Wiesenthal, J.; Leitner, W.; Klankermayer, J. Angew. Chem. Int. Ed. 2016, 55, 12266. doi: 10.1002/anie.201606427
8. [8]
  Aresta, M.; Dibenedetto, A.; Angelini, A. Chem. Rev. 2013, 114, 1709. doi: 10.1021/cr4002758
9. [9]
  Gao, P.; Li, S.; Bu, X.; Dang, S.; Liu, Z.; Wang, H.; Zhong, L.; Qiu, M.; Yang, C.; Cai, J. Nat. Chem. 2017, 9, 1019. doi: 10.1038/nchem.2794
10. [10]
  Kothandaraman, J.; Czaun, M.; Goeppert, A.; Haiges, R.; Jones, J. P.; May, R. B.; Prakash, G.; Olah, G. A. ChemSusChem 2015, 8, 1442. doi: 10.1002/cssc.201403458
11. [11]
  Li, C. W.; Ciston, J.; Kanan, M. W. Nature 2014, 508, 504. doi: 10.1038/nature13249
12. [12]
  Liu, Q.; Wu, L.; Jackstell, R.; Beller, M. Nat. Commun. 2015, 6, 5933. doi: 10.1038/ncomms6933
13. [13]
  Lian, Z.; Nielsen, D. U.; Lindhardt, A. T.; Daasbjerg, K.; Skrydstrup, T. Nat. Commun. 2016, 7, 13782. doi: 10.1038/ncomms13782
14. [14]
  Song, Q. -W.; Zhou, Z. -H.; He, L. -N. Green Chem. 2017, 19, 3707. doi: 10.1039/C7GC00199A
15. [15]
  Arlt, D.; Klein, G. Preparation of Nitriles from Formamides: U.S. Patent 4, 419, 297, 1983. http://www.whxb.pku.edu.cn/CN/Y2018/V34/I8/845
16. [16]
  Chen, B.-C.; Bednarz, M. S.; Zhao, R.; Sundeen, J. E.; Chen, P.; Shen, Z.; Skoumbourdis, A. P.; Barrish, J. C. Tetrahedron Lett. 2000, 41, 5453. doi: 10.1016/S0040-4039(00)00910-2
17. [17]
  Faraj, M. K. Synthesis of Isocyanate Precursors from Primary Formamides: U.S. Patent 5, 155, 267, 1992. doi: 10.3866/PKU.WHXB201701081
18. [18]
  Grant, H. G.; Summers, L. A. Aust. J. Chem. 1980, 33, 613. doi: 10.1071/CH9800613
19. [19]
  Han, Y.; Cai, L. Tetrahedron Lett. 1997, 38, 5423. doi: 10.1016/S0040-4039(97)01206-9
20. [20]
  Jackson, A.; Meth-Cohn, O. J. Chem. Soc., Chem. Commun. 1995, 1319. doi: 10.1039/C39950001319
21. [21]
  Kobayashi, K.; Nagato, S.; Kawakita, M.; Morikawa, O.; Konishi, H. Chem. Lett. 1995, 24, 575. doi: 10.1246/cl.1995.575
22. [22]
  Pettit, G.; Kalnins, M.; Liu, T.; Thomas, E.; Parent, K. J. Org. Chem. 1961, 26, 2563. doi: 10.1021/jo01351a623
23. [23]
  Kobayashi, S.; Yasuda, M.; Hachiya, I. Chem. Lett. 1996, 25, 407. doi: 10.1246/cl.1996.407
24. [24]
  Downie, I. M.; Earle, M. J.; Heaney, H.; Shuhaibar, K. F. Tetrahedron 1993, 49, 4015. doi: 10.1016/S0040-4020(01)89915-4
25. [25]
  Kobayashi, S.; Nishio, K. J. Org. Chem. 1994, 59, 6620. doi: 10.1021/jo00101a021
26. [26]
  Affan, M. A.; Jessop, P. G. Inorg. Chem. 2017, 56, 7301. doi: 10.1021/acs.inorgchem.7b01242
27. [27]
  Haynes, P.; Slaugh, L. H.; Kohnle, J. F. Tetrahedron Lett. 1970, 11, 365. doi: 10.1016/0040-4039(70)80086-7
28. [28]
  Schreiner, S.; James, Y. Y.; Vaska, L. Inorg. Chim. Acta 1988, 147, 139. doi: 10.1039/C39880000602
29. [29]
  Vaska, L.; Schreiner, S.; Felty, R. A.; Yu, J. Y. J. Mol. Catal. 1989, 52, L11. doi: 10.1016/0304-5102(89)80020-3
30. [30]
  Bi, Q. -Y.; Lin, J. -D.; Liu, Y. -M.; Xie, S. -H.; He, H. -Y.; Cao, Y. Chem. Commun. 2014, 50, 9138. doi: 10.1039/C4CC02973A
31. [31]
  Kudo, K.; Phala, H.; Sugita, N.; Takezaki, Y. Chem. Lett. 1977, 6, 1495. doi: 10.1246/cl.1977.1495
32. [32]
  Morimoto, Y.; Fujiwara, Y.; Taniguchi, H.; Hori, Y.; Nagano, Y. Tetrahedron Lett. 1986, 27, 1809. doi: 10.1016/S0040-4039(00)84381-6
33. [33]
  Cui, X.; Zhang, Y.; Deng, Y.; Shi, F. Chem. Commun. 2014, 50, 189. doi: 10.1039/C3CC46427J
34. [34]
  Molla, R. A.; Bhanja, P.; Ghosh, K.; Islam, S. S.; Bhaumik, A.; Islam, S. M. ChemCatChem 2017, 9, 1939. doi: 10.1039/C3CC46427J
35. [35]
  Zhang, Y.; Wang, H.; Yuan, H.; Shi, F. ACS Sustainable Chem. Eng. 2017, 5, 5758. doi: 10.1021/acssuschemeng.7b00363
36. [36]
  Ju, P.; Chen, J.; Chen, A.; Chen, L.; Yu, Y. ACS Sustainable Chem. Eng. 2017, 5, 2516. doi: 10.1021/acssuschemeng.6b02865
37. [37]
  Schreiner, S.; James, Y. Y.; Vaska, L. J. Chem. Soc., Chem. Commun. 1988, 602. doi: 10.1039/C39880000602
38. [38]
  Jessop, P. G.; Hsiao, Y.; Ikariya, T.; Noyori, R. J. Am. Chem. Soc. 1994, 116, 8851. doi: 10.1021/ja00098a072
39. [39]
  Kröcher, O.; Köppel, R. A.; Baiker, A. Chem. Commun. 1997, 453. doi: 10.1039/A608150I
40. [40]
  Munshi, P.; Heldebrant, D. J.; McKoon, E. P.; Kelly, P. A.; Tai, C. -C.; Jessop, P. G. Tetrahedron Lett. 2003, 44, 2725. doi: 10.1016/S0040-4039(03)00384-8
41. [41]
  Schmid, L.; Canonica, A.; Baiker, A. Appl. Catal., A: Chem. 2003, 255, 23. doi: 10.1016/S0926-860X(03)00641-0
42. [42]
  Rohr, M.; Grunwaldt, J.-D.; Baiker, A. J. Mol. Catal. A: Chem. 2005, 226, 253. doi: 10.1016/j.molcata.2004.10.037
43. [43]
  Rohr, M.; Grunwaldt, J.-D.; Baiker, A. J. Catal. 2005, 229, 144. doi: 10.1016/j.jcat.2004.09.026
44. [44]
  Zhang, L.; Han, Z.; Zhao, X.; Wang, Z.; Ding, K. Angew. Chem. Int. Ed., 2015, 54, 6186. doi: 10.1002/anie.201500939
45. [45]
  Kobayashi, K.; Kikuchi, T.; Kitagawa, S.; Tanaka, K. Angew. Chem. Int. Ed. 2014, 53, 11813. doi: 10.1002/anie.201406553
46. [46]
  Itagaki, S.; Yamaguchi, K.; Mizuno, N. J. Mol. Catal. A: Chem. 2013, 366, 347. doi: 10.1016/j.molcata.2012.10.014
47. [47]
  Farlow, M. W.; Adkins, H. J. Am. Chem. Soc. 1935, 57, 2222. doi: 10.1021/ja01314a054
48. [48]
  González-Sebastián, L.; Flores-Alamo, M.; Garcı́a, J. J Organometallics 2013, 32, 7186. doi: 10.1021/om400876j
49. [49]
  Minato, M.; Zhou, D. Y.; Sumiura, K. I.; Hirabayashi, R.; Yamaguchi, Y.; Ito, T. Chem. Commun. 2001, 2654. doi: 10.1039/B107837M
50. [50]
  Liu, J.; Guo, C.; Zhang, Z.; Jiang, T.; Liu, H.; Song, J.; Fan, H.; Han, B. Chem. Commun. 2010, 46, 5770. doi: 10.1039/C0CC00751J
51. [51]
  Liu, H.; Mei, Q.; Xu, Q.; Song, J.; Liu, H.; Han, B. Green Chem. 2017, 19, 196. doi: 10.1039/C6GC02243J
52. [52]
  Zhang, S.; Mei, Q.; Liu, H.; Liu, H.; Zhang, Z.; Han, B. RSC Adv. 2016, 6, 32370. doi: 10.1039/C6RA05199E
53. [53]
  Motokura, K.; Kashiwame, D.; Miyaji, A.; Baba, T. Org. Lett. 2012, 14, 2642. doi: 10.1021/ol301034j
54. [54]
  Motokura, K.; Kashiwame, D.; Takahashi, N.; Miyaji, A.; Baba, T. Chem. Eur. J. 2013, 19, 10030. doi: 10.1002/chem.201300935
55. [55]
  Motokura, K.; Takahashi, N.; Kashiwame, D.; Yamaguchi, S.; Miyaji, A.; Baba, T. Catal. Sci. Technol. 2013, 3, 2392. doi: 10.1039/C3CY00375B
56. [56]
  Motokura, K.; Takahashi, N.; Miyaji, A.; Sakamoto, Y.; Yamaguchi, S.; Baba, T. Tetrahedron 2014, 70, 6951. doi: 10.1016/j.tet.2014.07.089
57. [57]
  Shintani, R.; Nozaki, K.Organometallics 2013, 32, 2459. doi: 10.1021/om400175h
58. [58]
  Federsel, C.; Boddien, A.; Jackstell, R.; Jennerjahn, R.; Dyson, P. J.; Scopelliti, R.; Laurenczy, G.; Beller, M. Angew. Chem. Int. Ed. 2010, 49, 9777. doi: 10.1002/anie.201004263
59. [59]
  Ziebart, C.; Federsel, C.; Anbarasan, P.; Jackstell, R.; Baumann, W.; Spannenberg, A.; Beller, M. J. Am. Chem. Soc. 2012, 134, 20701. doi: 10.1021/ja307924a
60. [60]
  Frogneux, X.; Jacquet, O.; Cantat, T. Catal. Sci. Technol. 2014, 4, 1529. doi: 10.1039/C4CY00130C
61. [61]
  Federsel, C.; Ziebart, C.; Jackstell, R.; Baumann, W.; Beller, M. Chem. Eur. J. 2012, 18, 72. doi: 10.1002/chem.201101343
62. [62]
  Daw, P.; Chakraborty, S.; Leitus, G.; Diskin-Posner, Y.; Ben-David, Y.; Milstein, D. ACS Catal. 2017, 7, 2500. doi: 10.1021/acscatal.7b00116
63. [63]
  Yang, Z.-Z.; Yu, B.; Zhang, H.; Zhao, Y.; Ji, G.; Liu, Z. RSC Adv. 2015, 5, 19613. doi: 10.1039/C5RA00380F
64. [64]
  Luo, R.; Lin, X.; Chen, Y.; Zhang, W.; Zhou, X.; Ji, H. ChemSusChem 2017, 10, 1224. doi: 10.1002/cssc.201601490
65. [65]
  Luo, R.; Zhou, X.; Chen, S.; Li, Y.; Zhou, L.; Ji, H. Green Chem. 2014, 16, 1496. doi: 10.1039/C3GC42388C
66. [66]
  Nale, D. B.; Bhanage, B. M. Synlett 2016, 27, 1413. doi: 10.1055/s-0035-1561571
67. [67]
  Fang, C.; Lu, C.; Liu, M.; Zhu, Y.; Fu, Y.; Lin, B.-L. ACS Catal. 2016, 6, 7876. doi: 10.1021/acscatal.6b01856
68. [68]
  Das Neves Gomes, C.; Jacquet, O.; Villiers, C.; Thuéry, P.; Ephritikhine, M.; Cantat, T. Angew. Chem. Int. Ed. 2012, 51, 187. doi: 10.1002/anie.201105516
69. [69]
  Frogneux, X.; Blondiaux, E.; Thuéry, P.; Cantat, T. ACS Catal. 2015, 5, 3983. doi: 10.1021/acscatal.5b00734
70. [70]
  Villiers, C.; Dognon, J. P.; Pollet, R.; Thuéry, P.; Ephritikhine, M. Angew. Chem. Int. Ed. 2010, 49, 3465. doi: 10.1002/anie.201001035
71. [71]
  Riduan, S. N.; Zhang, Y.; Ying, J. Y. Angewandte Chemie 2009, 121, 3372. doi: 10.1002/ange.200806058
72. [72]
  Jacquet, O.; Das Neves Gomes, C.; Ephritikhine, M.; Cantat, T. J. Am. Chem. Soc. 2012, 134, 2934. doi: 10.1021/ja211527q
73. [73]
  Riduan, S. N.; Ying, J. Y.; Zhang, Y. J. Catal. 2016, 343, 46. doi: 10.1016/j.jcat.2015.09.009
74. [74]
  Chong, C. C.; Kinjo, R. Angew. Chem. 2015, 127, 12284. doi: 10.1002/ange.201505244
75. [75]
  Ortiz-Cervantes, C.; Flores-Alamo, M.; García, J. J. ACS Catal. 2015, 5, 1424. doi: 10.1021/cs5020095
76. [76]
  Song, J.; Zhou, B.; Liu, H.; Xie, C.; Meng, Q.; Zhang, Z.; Han, B. Green Chem. 2016, 18, 3956. doi: 10.1039/C6GC01455K
77. [77]
  Hao, L.; Zhao, Y.; Yu, B.; Yang, Z.; Zhang, H.; Han, B.; Gao, X.; Liu, Z. ACS Catal. 2015, 5, 4989. doi: 10.1021/acscatal.5b01274
78. [78]
  Dong, B.; Wang, L.; Zhao, S.; Ge, R.; Song, X.; Wang, Y.; Gao, Y. Chem. Commun. 2016, 52, 7082. doi: 10.1039/C6CC03058K
79. [79]
  Liu, X. F.; Li, X. Y.; Qiao, C.; Fu, H. C.; He, L. N. Angew. Chem. 2017, 129, 7533. doi: 10.1002/ange.201702734
80. [80]
  Xie, C.; Song, J.; Wu, H.; Zhou, B.; Wu, C.; Han, B. ACS Sustainable Chem. Eng. 2017, 5, 7086. doi: 10.1021/acssuschemeng.7b01287
81. [81]
  Liu, X. F.; Ma, R.; Qiao, C.; Cao, H.; He, L. N. Chem. Eur. J. 2016, 22, 16489. doi: 10.1002/chem.201603688
82. [82]
  Lv, H.; Xing, Q.; Yue, C.; Lei, Z.; Li, F. Chem. Commun. 2016, 52, 6545. doi: 10.1039/C6CC01234E
83. [83]
  Zhao, T. -X.; Zhai, G. -W.; Liang, J.; Li, P.; Hu, X. -B.; Wu, Y. -T. Chem. Commun. 2017, 53, 8046. doi: 10.1039/C7CC03860G

扫一扫看文章

计量

PDF下载量: 14
文章访问数: 1253
HTML全文浏览量: 118

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

二氧化碳和胺催化合成甲酰胺反应研究

通讯作者: 石峰, fshi@licp.cas.cn

English

Catalytic Synthesis of Formamides with Carbon Dioxide and Amines

Corresponding author: SHI Feng, fshi@licp.cas.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

二氧化碳和胺催化合成甲酰胺反应研究

通讯作者: 石峰, fshi@licp.cas.cn

English

Catalytic Synthesis of Formamides with Carbon Dioxide and Amines

Corresponding author: SHI Feng, fshi@licp.cas.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs