钯催化芳香硝基化合物与烯烃的选择性还原羰化酰胺化反应

引用本文: 杨莉, 石利军, 夏春谷, 李福伟. 钯催化芳香硝基化合物与烯烃的选择性还原羰化酰胺化反应[J]. 催化学报, 2020, 41(7): 1152-1160. doi: 10.1016/S1872-2067(20)63561-6 shu

Citation: Li Yang, Lijun Shi, Chungu Xia, Fuwei Li. Intermediate formation enabled regioselective access to amide in the Pd-catalyzed reductive aminocarbonylation of olefin with nitroarene[J]. Chinese Journal of Catalysis, 2020, 41(7): 1152-1160. doi: 10.1016/S1872-2067(20)63561-6 shu

钯催化芳香硝基化合物与烯烃的选择性还原羰化酰胺化反应

中国科学院兰州化学物理研究所, 羰基合成与选择氧化国家重点实验室, 甘肃兰州 730000
基金项目:
国家重点研发计划（2018YFB1501600）；国家自然科学基金（21773271，21972151）.

摘要: 与芳香胺相比,芳香硝基化合物具有廉价易得、官能团兼容性好等优点,作为氮源在下游含氮化学品合成中具有广泛的应用.目前烯烃羰化酰胺化反应绝大多数以胺类化合物为氮源,其中直链和支链酰胺产物的选择性主要是通过具有特定电子和位阻特性的配体调控实现.已报道的芳香硝基化合物的还原酰胺化反应研究中,需要外加还原剂或者利用金属羰基化合物Mo (CO)₆释放的CO为羰基源和还原剂.本文发展了一种毋须外加还原剂的钯催化芳香硝基化合物与烯烃的还原羰化酰胺化反应新方法.
研究发现,钯金属催化剂(特别是离子型)的抗衡阴离子是还原羰化酰胺化反应中化学选择性和羰化区域选择性的关键因素.抗衡阴离子为氯离子、硼酸为助剂时,最优钯前驱物K₂PdCl₄的产物主要为支链酰胺,此时不同的膦配体并不能调控其区域选择性,这与胺的烯烃酰胺化反应可以通过配体调控羰化的区域选择性表现出明显的不同.含氮中间体原位捕捉、硝基化合物还原下游可能中间体对照实验等研究表明,芳香硝基化合物在以一氧化碳为还原剂的催化还原体系下被完全脱氧还原为氮烯(Ar-N:),再经过烯酰胺中间体进一步烯键还原得到相应的支链酰胺;当离子型钯前驱物的抗衡阴离子配位性较弱时,最优钯前驱物为Pd (CH₃CN)₄(OTf)₂时,以直链酰胺为主要产物,此时不同的膦配体可以调控酰胺化的区域选择性.同样的机理研究表明,在该催化剂体系下芳香硝基化合物首先被还原为芳基胺,然后再发生与现有报道类似的胺类化合物的烯烃羰化酰胺化反应.这两个催化反应体系都表现出了较好的底物适用性,并且可以高效地应用于除草剂(敌稗)的一步合成.本文为以硝基化合物为起始氮源,通过催化控制生成特定含氮中间体,从而可控合成不同的含氮化学品提供了一条新思路.

关键词:

English

Intermediate formation enabled regioselective access to amide in the Pd-catalyzed reductive aminocarbonylation of olefin with nitroarene

State Key Laboratory for Oxo Synthesis and Selective Oxidation, Suzhou Research Institute of LICP, Lanzhou Institute of Chemical Physics (LICP), Chinese Academy of Sciences, Lanzhou 730000, Gansu, China
Received Date: 22 October 2019
Fund Project:
This work was funded by the National Key R&D Program of China (2018YFB1501600), the Natural Science Foundation of China (21773271, 21972151).

Abstract: An efficient route for the palladium-catalyzed reductive aminocarbonylation of olefins with nitroarenes was developed using carbon monoxide (CO) as both reductant and carbonyl source, which enables facile access to amides with excellent regioselectivity and broad substrate scope. It is found that the counter anions of the Pd catalyst precursors significantly affect the reaction chemoselectivity and amide regioselectivity. Branched amides were mainly obtained with K₂PdCl₄ as the metal catalyst, and phosphine ligands had no influence on the regioselectivity but affected the catalytic reactivity. However, phosphine ligands had significant effects on aminocarbonylation regioselectivity when Pd(CH₃CN)₄(OTf)₂ was used; monodentate phosphines tended to form branched amides, and bidentate phosphines mainly formed linear amides. Trapping experiments, primary kinetic studies, and control reactions with all possible N-species reduced from nitroarene indicated that the catalytic synthesis of branched and linear amides produced nitrene (further converted to enamide) and aniline, respectively, different from the previous ligand-controlled regioselective synthesis of amides via the aminocarbonylation of olefins with amines. Furthermore, the proposed synthesis route could be applied in the synthesis of gram-scale propanil under mild conditions.

Key words:

1. [1] J. S. Zhu, C. J. Li, K. Y. Tsui, N. Kraemer, J.-H. Son, M. J. Haddadin, D. J. Tantillo, M. J. Kurth, J. Am. Chem. Soc., 2019, 141, 6247-6253.
2. [2] M. Rauser, R. Eckert, M. Gerbershagen, M. Niggemann, Angew. Chem. Int. Ed., 2019, 58, 6713-6717.
3. [3] J. H. Gui, C. M. Pan, Y. Jin, T. Qin, J. C. Lo, B. J. Lee, S. H. Spergel, M. E. Mertzman, W. J. Pitts, T. E. L. Cruz, M. A. Schmidt, N. Darvatkar, S. R. Natarajan, P. S. Baran, Science, 2015, 348, 886-891.
4. [4] N. Ono, The Nitro Group in Organic Synthesis, Wiley-VCH, Weinheim, 2001, 1-2.
5. [5] C. W. Cheung, J. A. Ma, X. L. Hu, J. Am. Chem. Soc., 2018, 140, 6789-6792.
6. [6] T. V. Nykaza, A. Ramirez, T. S. Harrison, M. R. Luzung, A. T. Radosevich, J. Am. Chem. Soc., 2018, 140, 3103-3113.
7. [7] C. W. Cheung, M. L. Ploeger, X. L. Hu, Nat. Commun., 2017, 8, 14878-14887.
8. [8] M. Shevlin, X. Y. Guan, T. G. Driver, ACS Catal., 2017, 7, 5518-5522.
9. [9] C. W. Cheung, M. L. Ploeger, X. L. Hu, ACS Catal., 2017, 7, 7092-7096.
10. [10] R. Rubio-Presa, M. R. Pedrosa, M. A. Fernandez-Rodríguez, F. J. Arnaiz, R. Sanz, Org. Lett., 2017, 19, 5470-5473.
11. [11] Z. C. Lin, Z. Y. Hu, X. Zhang, J. H. Dong, J. B. Liu, D. Z. Chen, X. X. Xu, Org. Lett., 2017, 19, 5284-5287.
12. [12] M. Rauser, C. Ascheberg, M. Niggemann, Angew. Chem. Int. Ed., 2017, 56, 11570-11574.
13. [13] C. W. Cheung, X. L. Hu, Nat. Commun., 2016, 7, 12494.
14. [14] K. L. Zhu, M. P. Shaver, S. P. Thomas, Chem. Sci., 2016, 7, 3031-3035.
15. [15] N. Jana, F. Zhou, T. G. Driver, J. Am. Chem. Soc., 2015, 137, 6738-6741.
16. [16] T. J. Mooibroek, E. Bouwman, E. Drent, Organometallics, 2012, 31, 4142-4156.
17. [17] T. J. Mooibroek, L. Schoon, E. Bouwman, E. Drent, Chem. Eur. J., 2011, 17, 13318-13333.
18. [18] K.-S. Ju, R. E. Parales, Microbiol. Mol. Biol. Rev., 2010, 74, 250-272.
19. [19] A. M. Tafesh, J. Weiguny, Chem. Rev., 1996, 96, 2035-2052.
20. [20] R. M. Figueiredo, J. S. Suppo, J. M. Campagne, Chem. Rev., 2016, 116, 12029-12122.
21. [21] V. R. Pattabiraman, J. W. Bode, Nature, 2011, 480, 471-479.
22. [22] Q. J. Yuan, M. S. Sigman, J. Am. Chem. Soc., 2018, 140, 6527-6530.
23. [23] X. G. Guo, A. Facchetti, T. J. Marks, Chem. Rev., 2014, 114, 8943-9021.
24. [24] J. B. Peng, H. Q. Geng, F. P. Wu, D. Li, X.-F. Wu, J. Catal., 2019, 375, 519-523.
25. [25] J. W. Li, S. Y. Wang, S. C. Zou, H. M. Huang, Commun. Chem., 2019, 2, 1-9.
26. [26] B. Gao, G. Y. Zhang, X. B. Zhou, H. M. Huang, Chem. Sci., 2018, 9, 380-386.
27. [27] L. Yang, L. J. Shi, Q. Xing, K. W. Huang, C. G. Xia, F. W. Li, ACS Catal., 2018, 8, 10340-10348.
28. [28] F. Sha, H. Alper, ACS Catal., 2017, 7, 2220-2229.
29. [29] J. Liu, H. Q. Li, A. Spannenberg, R. Franke, R. Jackstell, M. Beller, Angew. Chem. Int. Ed., 2016, 55, 13544-13548.
30. [30] T. Y. Xu, F. Sha, H. Alper, J. Am. Chem. Soc., 2016, 138, 6629-6635.
31. [31] X. Y. Li, X. W. Li, N. Jiao, J. Am. Chem. Soc., 2015, 137, 9246-9249.
32. [32] H. Q. Li, K. W. Dong, H. Neumann, M. Beller, Angew. Chem. Int. Ed., 2015, 54, 10239-10243.
33. [33] G. Y. Zhang, B. Gao, H. M. Huang, Angew. Chem. Int. Ed., 2015, 54, 7657-7661.
34. [34] K. W. Dong, X. J. Fang, R. Jackstell, G. Laurenczy, Y. H. Li, M. Beller, J. Am. Chem. Soc., 2015, 137, 6053-6058.
35. [35] X. J. Fang, R. Jackstell, M. Beller, Angew. Chem., Int. Ed., 2013, 52, 14089-14093.
36. [36] J. B. Peng, H. Q. Geng, D. Li, X. X. Qi, J. Ying, X. F. Wu, Org. Lett., 2018, 20, 4988-4993.
37. [37] F. Zhou, D. S. Wang, X. Y. Guan, T. G. Driver, Angew. Chem. Int. Ed., 2017, 56, 4530-4534.
38. [38] C. W. Cheung, M. Leendert Ploeger, X. L. Hu, Chem. Sci., 2018, 9, 655-659.
39. [39] H. R. Liang, L. Zhang, X. L. Zheng, H. Y. Fu, M. L. Yuan, R. X. Li, H. Chen, Chin. J. Catal., 2012, 33, 977-981.
40. [40] A. C. Brezny, C. R. Landis, J. Am. Chem. Soc., 2017, 139, 2778-2785.
41. [41] W. L. Ren, W. J. Chang, J. Dai, Y. Shi, J. F. Li, Y. A. Shi, J. Am. Chem. Soc., 2016, 138, 14864-14867.
42. [42] D. Semeril, C. Jeunesse, D. Matt, L. Toupet, Angew. Chem. Int. Ed., 2006, 45, 5810-5814.
43. [43] S. C. Bourque, F. Maltais, W. J. Xiao, O. Tardif, H. Alper, P. Arya, L. E. Manzer, J. Am. Chem. Soc., 1999, 121, 3035-3038.
44. [44] J. B. Peng, X. F. Wu, Angew. Chem. Int. Ed., 2018, 57, 1152-1160.
45. [45] D. Ding, G. H. Zhu, X. F. Jiang, Angew. Chem. Int. Ed., 2018, 57, 9028-9032.
46. [46] D. Ding, T. Mou, M. H. Feng, X. F. Jiang, J. Am. Chem. Soc., 2016, 138, 5218-5221.
47. [47] M. H. Feng, B. Q. Tang, N. Z. Wang, H. X. Xu, X. F. Jiang, Angew. Chem. Int. Ed., 2015, 54, 14960-14964.
48. [48] H. Q. Li, K. W. Dong, H. J. Jiao, H. Neumann, R. Jackstell, M. Beller, Nat. Chem., 2016, 8, 1159-1166.
49. [49] M. Beller, J. Seayad, A. Tillack, H. J. Jiao, Angew. Chem. Int. Ed., 2004, 43, 3368-3398.
50. [50] S. Matsunaka, Science, 1968, 160, 1360-1361.
51. [51] A. Vavasori, L. Ronchin, Pure Appl. Chem., 2012, 84, 473-484.
52. [52] Y. Takebayashi, K. Suea, S. Yodaa, T. Furuyaa, K. Mae, Chem. Eng. J., 2012, 180, 250-254.
53. [53] F. Ragaini, M. Gasperini, S. Cenini, L. Arnera, A. Caselli, P. Macchi, N. Casati, Chem. Eur. J., 2009, 15, 8064-8077.
54. [54] F. Paul, Coord. Chem. Rev., 2000, 203, 269-323.
55. [55] R. Waterman, G. L. Hillhouse, J. Am. Chem. Soc., 2003, 125, 13350-13351.
56. [56] S. M. Bellows, N. A. Arnet, P. M. Gurubasavaraj, W. W. Brennessel, E. Bill, T. R. Cundari, P. L. Holland, J. Am. Chem. Soc., 2016, 138, 12112-12123.
57. [57] M. A. Aubart, R. G. Bergman, Organometallics, 1999, 18, 811-813.
58. [58] C. Amatore, E. Carre, A. Jutand, M. A. M'Barki, Organometallics, 1995, 14, 1818-1826.

扫一扫看文章

计量

PDF下载量: 205
文章访问数: 781
HTML全文浏览量: 132

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

钯催化芳香硝基化合物与烯烃的选择性还原羰化酰胺化反应

English

Intermediate formation enabled regioselective access to amide in the Pd-catalyzed reductive aminocarbonylation of olefin with nitroarene

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

钯催化芳香硝基化合物与烯烃的选择性还原羰化酰胺化反应

English

Intermediate formation enabled regioselective access to amide in the Pd-catalyzed reductive aminocarbonylation of olefin with nitroarene

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