Boron-Promoted Co-Catalyzed N-Methylation of Secondary Aromatic Amines with CO2 and H2

doi:10.6023/cjoc202405049

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (10): 3233-3240.DOI: 10.6023/cjoc202405049 Previous Articles Next Articles

Special Issue: 二氧化碳专题合集

ARTICLES

硼促进Co催化使用CO₂和H₂实现仲芳香胺N-甲基化

石亲^a^,^b, 李臻^a, 何林^a^,^*(), 李玉东^a^,^*(), 李跃辉^c^,^*()

a 中国科学院兰州化学物理研究所低碳催化与二氧化碳利用国家重点实验室(筹) 羰基合成与选择氧化国家重点实验室兰州 730000
b 中国科学院大学北京 100049
c 上海交通大学国家电投智慧能源创新学院上海 200240

收稿日期:2024-05-31 修回日期:2024-07-16 发布日期:2024-08-16
基金资助:
国家自然科学基金(22022204); 国家自然科学基金(22102197); 江苏省国家自然基金(BK20211096); 江苏省国家自然基金(BK20211093)

Boron-Promoted Co-Catalyzed N-Methylation of Secondary Aromatic Amines with CO₂ and H₂

Qin Shi^a^,^b, Zhen Li^a, Lin He^a,*(), Yudong Li^a,*(), Yuehui Li^c,*()

a State Key Laboratory of Low Carbon Catalysis and Carbon Dioxide Utilization; State Key Laboratory for Oxo Synthesis and Selective Oxidation, Lanzhou Institute of Chemical Physics, Chinese Academy of Sciences, Lanzhou 730000
b University of Chinese Academy of Sciences, Beijing 100049
c College of Smart Energy, Shanghai Jiao Tong University, Shanghai 200240

Received:2024-05-31 Revised:2024-07-16 Published:2024-08-16
Contact: *E-mail: liyuehui@sjtu.edu.cn;liyd@ms.xjb.ac.cn;helin@licp.cas.cn
Supported by:
National Natural Science Foundation of China(22022204); National Natural Science Foundation of China(22102197); National Science Foundation of Jiangsu Province(BK20211096); National Science Foundation of Jiangsu Province(BK20211093)

1. .pdf(1130KB)

Abstract

Development of catalytic methods using CO₂/H₂ as methylating reagent for selective methylation of amines is highly attractive. Herein, the methylation of N—H bond via boron promoted activation of Co-formate intermediates is reported. This catalytic system showed excellent functional group tolerance with high catalytic activity, and a series of methylated products were acquired in moderate to excellent yields under mild conditions (e.g. 80 ℃ or 60 ℃). It was inferred that imine complex C was the crucial intermediate formed via dehydration of species B, providing efficient C—N coupling for the selective N-methylation of secondary aromatic amines with CO₂/H₂.

Key words: CO₂/H₂, N-methylation, cobalt catalysis

Cite this article

Qin Shi, Zhen Li, Lin He, Yudong Li, Yuehui Li. Boron-Promoted Co-Catalyzed N-Methylation of Secondary Aromatic Amines with CO₂ and H₂[J]. Chinese Journal of Organic Chemistry, 2024, 44(10): 3233-3240.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 5

References 42

[1]	(a) Chatterjee, J.; Rechenmacher, F.; Kessler, H. Angew. Chem., Int. Ed. 2013, 52, 254. pmid: 25255204
	(b) Vitaku, E.; Smith, D. T.; Njardarson, J. T. J. Med. Chem. 2014, 57, 10257. doi: 10.1021/jm501100b pmid: 25255204
[2]	(a) Malkov, A. V.; Vranková, K.; Cerny, M.; Kocovsky, P. J. Org. Chem. 2009, 74, 8425.
	(b) Fatemeh, N. H.; Farasat, Z.; Nabavizadeh, S. M.; Wu, G.; Abu-Omar, M. M. J. Orgnomet. Chem. 2019, 880, 232.
[3]	Atkinson, B. N.; Williams, J. M. J. ChemCatChem 2014, 6, 1860.
[4]	(a) Auerbach, J.; Zamore, M.; Weinreb, S. M. J. Org. Chem. 1976, 41, 725.
	(b) Basha, A.; Orlando, J.; Weinreb, S. M. Synth. Commun. 1977, 7, 549.
[5]	(a) Schäffner, B.; Schäffner, F.; Verevkin, S. P.; Börner, A. Chem. Rev. 2010, 110, 4554. doi: 10.1021/cr900393d pmid: 20345182
	(b) Ji, Y.; Sweeney, J.; Zoglio, J.; Gorin, D. J. J. Org. Chem. 2013, 78, 11606. pmid: 20345182
	(c) Fiorani, G.; Perosa, A.; Selva, M. Green Chem. 2018, 20, 288. pmid: 20345182
[6]	Alenazi, N. A.; Lai, E. P. C.; Manthorpe, J. M. J. Mol. Recognit. 2014, 27, 755.
[7]	Méndez, M. V.; Heredia, D. A.; Larghi, E. L.; Bracca, A. B. J.; Kaufman, T. S. RSC Adv. 2017, 7, 28298.
[8]	Kaithal, A.; Hölscher, M.; Leitner, W. Chem. Sci. 2021, 12, 976.
[9]	(a) Garces, L. J.; Makwana, V. D.; Hincapie, B.; Sacco, A.; Suib, S. L. J. Catal. 2003, 217, 107. pmid: 29039671
	(b) Liu, Z.; Yang, Z.; Yu, X.; Zhang, H.; Yu, B.; Zhao, Y.; Liu, Z. Adv. Synth. Catal. 2017, 359, 4278. pmid: 29039671
	(c) Tsarev, V. N.; Morioka, Y.; Caner, J.; Wang, Q.; Ushimaru, R.; Kudo, A.; Naka, H.; Saito, S. Org. Lett. 2015, 17, 2530. pmid: 29039671
	(d) Liang, R.; Li, S.; Wang, R.; Lu, L.; Li, F. Org. Lett. 2017, 19, 5790. doi: 10.1021/acs.orglett.7b02723 pmid: 29039671
[10]	(a) Guo, Z.; Zhang, B.; Wei, X.; Xi, C. ChemSusChem 2018, 11, 2296.
	(b) Maji, S.; Das, A.; Mandal, S. K. Chem. Sci. 2021, 12, 12174.
	(c) Zou, Q.; Long, G.; Zhao, T.; Hu, X. Green Chem. 2020, 22, 1134.
[11]	(a) Artz, J.; Müller, T. E.; Thenert, K.; Kleinekorte, J.; Meys, R.; Sternberg, A.; Bardow, A.; Leitner, W. Chem. Rev. 2018, 118, 434.
	(b) Shindell, D.; Smith, C. J. Nature 2019, 573, 408.
	(c) Figueres, C.; Le, Quéré, C.; Mahindra, A.; Bäte, O.; Whiteman, G.; Peters, G.; Guan, D. Nature 2018, 564, 27.
[12]	(a) Ren, X.; Zheng, Z.; Zhang, L.; Wang, Z.; Xia, C.; Ding, K. Angew. Chem., Int. Ed. 2017, 56, 310.
	(b) Hua, K.; Liu, X.; Wei, B.; Shao, Z.; Deng, Y.; Zhong, L.; Wang, H.; Sun, Y. Green Chem. 2021, 23, 8040.
[13]	(a) Xia, S.-P.; Ding, G.-R.; Zhang, R.; Han, L.-J.; Xu, B.-H.; Zhang, S.-J. Green Chem. 2021, 23, 3073.
	(b) Yang, J.; Liu, J.; Ge, Y.; Huang, W.; Schneider, C.; Dühren, R.; Franke, R.; Neumann, H.; Jackstell, R.; Beller, M. Chem. Commun. 2020, 56, 5235.
	(c) Gehrtz, P. H.; Hirschbeck, V.; Fleischer, I. Chem. Commun. 2015, 51, 12574.
	(d) Khan, M. U.; Khan, S. U.; Kiriratnikom, J.; Zareen, S.; Zhang, X. Chin. Chem. Lett. 2022, 33, 1081.
[14]	(a) Yang, D.-T.; Zhu, M.; Schiffer, Z. J.; Williams, K.; Song, X.; Liu, X.; Manthiram, K. ACS Catal. 2019, 9, 4699.
	(b) Jiang, Y.-X.; Liao, L.-L.; Gao, T.-Y.; Xu, W.-H. Zhang, W.; Song, L.; Sun, G.-Q.; Ye, J.-H.; Lan, Y.; Yu, D.-G. Nat. Synth. 2024, 3, 394.
[15]	(a) Wang, H.; Li, Y.; Sun, Y.; Li, Y. J. Org. Chem. 2023, 88, 8835.
	(b) Wang, H.; Li, C.; Li, Y.; Chen, J.; Liu, S.; Li, Y.; Org. Chem. Front. 2024, 11, 1322.
[16]	(a) Huang, Y.; Wang, Y.; Wu, Y.; Yu, Y.; Zhang, B. Sci. China Chem. 2022, 65, 204.
	(b) Wang, M.; Chu, L.-Y.; Li, Z.-Y.; Messinis, A. M.; Ding, Y.-Q.; Hu, L.; Ma, J.-B. J. Phys. Chem. Lett. 2021, 12, 3490.
	(c) Brahmayya, M.; Dai, S. A.; Suen, S.-Y. J. CO₂ Util. 2017, 22, 135.
	(d) Du, C.; Chen, Y. Chin. J. Chem. 2020, 38, 1057.
	(e) Du, C.; Chen, Y. Acta Chim. Sinica 2020, 78, 938. (in Chinese)
	(杜重阳, 陈耀峰, 化学学报, 2020, 78, 938.) doi: 10.6023/A20060268
[17]	(a) Dong, Y.; Yang, P.; Zhao, S.; Li, Y. Nat. Commun. 2020, 11, 4096.
	(b) Wang, H.; Dong, Y.; Zheng, C.; Sandoval, C. A.; Wang, X.; Makha, M.; Li, Y. Chem 2018, 4, 2883.
	(c) Wang, H.; Li, Y.; Liu, S.; Makha, M.; Bai, J.-F.; Li, Y. ChemSusChem 2022, 15, e202200227.
	(d) Jiang, X.; Huang, Z.; Makha, M.; Du, C.-X.; Zhao, D.; Wang, F.; Li, Y. Green Chem. 2020, 22, 5317.
	(e) Huang, Z.; Jiang, X.; Zhou, S.; Yang, P.; Du, C.-X.; Li, Y. ChemSusChem 2019, 12, 3054.
	(f) Du, M.; Sun, Y.; Zhao, J.; Hu, H.; Sun, L.; Li, Y. Chin. Chem. Lett. 2023, 34, 108269.
	(g) Wang, T.; Yang, J.; Chen, J.; He, Q.; Li, Z.; Lei, L.; Lu, J.; Leung, M. K. H.; Yang, B.; Hou, Y. Chin. Chem. Lett. 2020, 31, 1438.
	(h) Liu, Y.; Yang, H.; Fan, X.; Shan, B.; Meyer, T. J. Chin. Chem. Lett. 2022, 33, 4691.
[18]	(a) Ma, S.-S.; Sun, R.; Zhang, Z.-H.; Guan, P.-X.; Lin, J.-Q.; Li, C.-S.; Xu, B.-H. Green Chem. 2023, 25, 8625.
	(b) Ren, C.; Terazzi, C.; Werner, T. Green Chem. 2023, 26, 439.
	(c) Murata, T.; Hiyoshi, M.; Maekawa, S.; Saiki, Y.; Ratanasak, M.; Hasegawa, J.; Ema, T. Green Chem. 2022, 24, 2385.
	(d) Zou, Q.; Yi, Y.; Zhao, T.; Liu, F.; Kang, C.; Hu, X. J. CO₂ Util. 2021, 50, 101590.
	(e) Xia, H.-M.; Zhang, F.-L.; Ye, T.; Wang, Y.-F. Angew. Chem., nt. Ed. 2018, 57, 11770.
	(f) Zhang, H.; Zhang, Y.; Gao, K. Org. Chem. Front. 2023, 10, 2491.
[19]	Li, Y.; Fang, X.; Junge, K.; Beller, M. Angew. Chem., Int. Ed. 2013, 52, 9568.
[20]	Ren, C.; Terazzi, C.; Werner, T. Green Chem. 2024, 26, 439.
[21]	Beydoun, K.; vom Stein, T.; Klankermayer, J.; Leitner, W. Angew. Chem., Int. Ed. 2013, 52, 9554.
[22]	Li, Y.; Sorribes, I.; Yan, T.; Junge, K.; Beller, M. Angew. Chem., Int. Ed. 2013, 52, 12156.
[23]	(a) He, Z.; Liu, H.; Qian, Q.; Lu, L.; Guo, W.; Zhang, L.; Han, B. Sci. China Chem. 2017, 60, 927.
	(b) Paul, B.; Panja, D.; Kundu, S. Org. Lett. 2019, 21, 5843.
	(c) Dang, T.; Ramalingam, B.; Seayad, A. M. ACS Catal. 2015, 5, 4082.
	(d) Huang, M.; Cai, X.; Liu, Y.; Ke, Z. Chin. Chem. Lett. 2024, 35, 109323.
[24]	Toyao, T.; Siddiki, S. M. A. H.; Morita, Y.; Kamachi, T.; Touchy, A. S.; Onodera, W.; Kon, K.; Furukawa, S.; Ariga, H.; Asakura, K.; Yoshizawa, K.; Shimizu, K.-I. Chem.-Eur. J. 2017, 23, 14848.
[25]	Jo, E.-A.; Lee, J.-H.; Jun, C.-H. Chem. Commun. 2008, 44, 5779.
[26]	(a) Wang, L.-M.; Jenkinson, K.; Wheatley, A. E. H.; Kuwata, K.; Saito, S.; Naka, H. ACS Sustainable Chem. Eng. 2018, 6, 15419.
	(b) Cui, X.; Zhang, Y.; Deng, Y.; Shi, F. Chem. Commun. 2014, 50, 13521.
	(c) Cho, J. H.; Ha, Y.; Cho, A.; Park, J.; Choi, J.; Won, Y.; Kim, H.; Kim, B. M. Catal. Sci. Technol. 2022, 12, 3524.
	(d) Saito, Y.; Senzaki, T.; Nishizawa, K.; Kobayashi, S. Green Chem. 2023, 25, 7524.
[27]	(a) Toyao, T.; Siddiki, S. M. A. H.; Ishihara, K.; Kon, K.; Onodera, W.; Shimizu, K. Chem. Lett. 2017, 46, 68.
	(b) Zhu, L.; Wang, L.-S.; Li, B.; Li, W.; Fu, B. Catal. Sci. Technol. 2016, 6, 6172.
[28]	Du, X.-L.; Tang, G.; Bao, H.-L.; Jiang, Z.; Zhong, Z.-H.; Su, D.; Wang, J.-Q. ChemSusChem 2015, 8, 3489.
[29]	Ke, Z.; Zhao, Y.; Li, R.; Wang, H.; Zeng, W.; Tang, M.; Han, B.; Liu, Z. Green Chem. 2021, 23, 9147.
[30]	Shi, Q.; Hu, H.; Du, M.; Sun, Y.; Li, Y.; Li, Y. Org. Lett. 2023, 25, 7100.
[31]	Fu, M.-C.; Shang, R.; Cheng, W.-M.; Fu, Y. Angew. Chem., Int. Ed. 2015, 54, 9042.
[32]	Zhang, Q.; Lin, X.-T.; Fukaya, N.; Fujitani, T.; Sato, K.; Choi, J.-C. Green Chem. 2021, 22, 8414.
[33]	Li, X.-D.; Xia, S.-M.; Chen, K.-H.; Liu, X.-F.; Li, H.-R.; He, L.-N. Green Chem. 2018, 20, 4853.
[34]	Li, J.; Huang, C.; Wen, D.; Zheng, Q.; Tu, B.; Tu, T. Org. Lett. 2021, 23, 687.
[35]	Larionova, N. A.; Ondozabal, J. M.; Smith, E. G.; Cambeiro, X. C. Org. Lett. 2021, 23, 5383. doi: 10.1021/acs.orglett.1c01715 pmid: 34197124
[36]	Yamada, S.; Gavryushin, A.; Knochel, P. Angew. Chem., nt. Ed. 2010, 49, 2215.
[37]	Xu, Y.; Zhang, Z.; Qiu, C.; Chen, S.; Ling, X.; Su, C. ChemSusChem 2020, 14, 582.
[38]	Chen, Z.; Zeng, H.; Gong, H.; Wang, H.; Li, C.-J. Chem. Sci. 2015, 6, 4174.
[39]	Jiang, X.; Wang, C.; Wei, Y.; Xue, D.; Liu, Z.; Xiao, J. Chem.-Eur. J. 2014, 20, 58. doi: 10.1002/chem.201303802 pmid: 24327323
[40]	Basak, S.; Alvarez-Montoya, A.; Winfrey, L.; Melen, R. L.; Pulis, A. P. ACS. Catal. 2020, 10, 4835.
[41]	Matsumoto, K.; Yoshida, M.; Shindo, M. Angew. Chem., Int. Ed. 2016, 55, 5272.
[42]	Paquette, L. A.; Kuhla, D. E.; Barrett, J. H. J. Org. Chem. 1969, 34, 2879.

Entry	Additive	Solvent	Yield^b/%
1	—	THF	n.d.
2	B(C₆F₅)₃	THF	35
3	MSA	THF	Trace
4	Al(OTf)₃	THF	n.d.
5	Sn(OTf)₃	THF	n.d.
6	Zn(OTf)₂	THF	n.d.
7	B(C₆F₅)₃	1,4-Dioxane	42
8	B(C₆F₅)₃	EtOH	27
9	B(C₆F₅)₃	Toluene	Trace
10	B(C₆F₅)₃	CH₃CN	Trace
11^c	B(C₆F₅)₃	1,4-Dioxane	60
12^c^,^d	B(C₆F₅)₃	1,4-Dioxane	75
13^c^,^e	B(C₆F₅)₃	1,4-Dioxane	81
14^f	B(C₆F₅)₃	1,4-Dioxane	n.d.
15^g	B(C₆F₅)₃	1,4-Dioxane	n.d.

Entry	Additive	Solvent	Yield^b/%
1	—	THF	n.d.
2	B(C₆F₅)₃	THF	35
3	MSA	THF	Trace
4	Al(OTf)₃	THF	n.d.
5	Sn(OTf)₃	THF	n.d.
6	Zn(OTf)₂	THF	n.d.
7	B(C₆F₅)₃	1,4-Dioxane	42
8	B(C₆F₅)₃	EtOH	27
9	B(C₆F₅)₃	Toluene	Trace
10	B(C₆F₅)₃	CH₃CN	Trace
11^c	B(C₆F₅)₃	1,4-Dioxane	60
12^c^,^d	B(C₆F₅)₃	1,4-Dioxane	75
13^c^,^e	B(C₆F₅)₃	1,4-Dioxane	81
14^f	B(C₆F₅)₃	1,4-Dioxane	n.d.
15^g	B(C₆F₅)₃	1,4-Dioxane	n.d.

硼促进Co催化使用CO₂和H₂实现仲芳香胺N-甲基化

Boron-Promoted Co-Catalyzed N-Methylation of Secondary Aromatic Amines with CO₂ and H₂

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 5

References 42

Related Articles 4

Recommended Articles

Metrics

Comments

[1]	Jiayan Du, Juntao Liu, Guixia Liu, Zheng Huang. Cobalt-Catalyzed Regio- and Stereoselective Isomerization of Terminal Alkenes to trans-2-Alkenes [J]. Chinese Journal of Organic Chemistry, 2024, 44(9): 2889-2897.
[2]	Shiquan Gao, Chuangjun Liu, Junfeng Yang, Junliang Zhang. Cobalt-Catalyzed Electrochemical Reductive Coupling of Alkynes and Alkenes [J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1559-1565.
[3]	Yinyin Wang, Xiaowan Lin, Piao Zhang, Meihua Shen, Huadong Xu, Defeng Xu. Design and Synthesis of Pyridine and 1,3,5-Triazine PNP Pincer Ligands and Their Application in Cobalt Catalyzed Semihydrogenation of Terminal Alkynes [J]. Chinese Journal of Organic Chemistry, 2021, 41(8): 3312-3320.
[4]	Sun Yiming, Ding Qifeng, Yu Yang, He Yide, Huang Fei. Progress in Co-Catalyzed C-H Amination [J]. Chinese Journal of Organic Chemistry, 2019, 39(12): 3363-3374.

硼促进Co催化使用CO2和H2实现仲芳香胺N-甲基化