硼促进Co催化使用CO2和H2实现仲芳香胺N-甲基化

doi:10.6023/cjoc202405049

有机化学 ›› 2024, Vol. 44 ›› Issue (10): 3233-3240.DOI: 10.6023/cjoc202405049 上一篇下一篇

研究论文

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
通讯作者: 何林, 李玉东, 李跃辉
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: Lin He, Yudong Li, Yuehui Li
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)

文章分享

1. 243233S.pdf(1130KB)

摘要/Abstract

以CO₂/H₂为新型甲基化试剂, 对于发展绿色甲基化方法, 建立高效CO₂利用新体系具有重要意义. 本工作基于硼活化甲酸根钴中间体策略, 以爪型三膦配体Triphos原位与Co形成催化剂, 实现了温和条件下的N—H甲基化反应. 该体系适用于芳香二级胺类底物, 并表现出优秀的化学选择性和官能团兼容性, 在60~80 ℃反应条件下, 对25个底物反应获得了38%~96%的收率. 基于对照实验结果推测, Lewis酸通过B—O相互作用活化甲酸钴物种, 接受胺分子的亲核进攻生成物种B, 之后脱水生成反应的关键中间体C.

关键词: 二氧化碳/氢气, N-甲基化反应, 钴催化

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

引用此文

石亲, 李臻, 何林, 李玉东, 李跃辉. 硼促进Co催化使用CO₂和H₂实现仲芳香胺N-甲基化[J]. 有机化学, 2024, 44(10): 3233-3240.

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.

导出引用 EndNote|Reference Manager|ProCite|BibTeX|RefWorks

分享此文

图/表 5

参考文献 42

[1]	(a) Chatterjee, J.; Rechenmacher, F.; Kessler, H. Angew. Chem., Int. Ed. 2013, 52, 254.
	(b) Vitaku, E.; Smith, D. T.; Njardarson, J. T. J. Med. Chem. 2014, 57, 10257.
[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.
	(b) Ji, Y.; Sweeney, J.; Zoglio, J.; Gorin, D. J. J. Org. Chem. 2013, 78, 11606.
	(c) Fiorani, G.; Perosa, A.; Selva, M. Green Chem. 2018, 20, 288.
[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.
	(b) Liu, Z.; Yang, Z.; Yu, X.; Zhang, H.; Yu, B.; Zhao, Y.; Liu, Z. Adv. Synth. Catal. 2017, 359, 4278.
	(c) Tsarev, V. N.; Morioka, Y.; Caner, J.; Wang, Q.; Ushimaru, R.; Kudo, A.; Naka, H.; Saito, S. Org. Lett. 2015, 17, 2530.
	(d) Liang, R.; Li, S.; Wang, R.; Lu, L.; Li, F. Org. Lett. 2017, 19, 5790.
[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.)
[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.
[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.
[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

补充材料

可视化

摘要/Abstract

引用此文

分享此文

图/表 5

参考文献 42

相关文章 12

编辑推荐

相关统计

本文评价

[1]	杜佳言, 刘俊涛, 刘桂霞, 黄正. 钴催化末端烯烃区域和立体选择性异构合成反式-2-烯烃[J]. 有机化学, 2024, 44(9): 2889-2897.
[2]	贝文峰, 潘健, 冉冬梅, 刘伊琳, 杨震, 冯若昆. 基于钴催化吲哚酰胺与二炔和单炔的[4+2]环化反应合成γ-咔啉酮[J]. 有机化学, 2023, 43(9): 3226-3238.
[3]	高师泉, 刘闯军, 杨俊锋, 张俊良. 钴催化的烯烃和炔烃的电化学还原偶联反应[J]. 有机化学, 2023, 43(4): 1559-1565.
[4]	周鹏, 朱伟明, 张建涛, 肖朵朵, 郭祥峰, 刘卫兵. 钴催化芳基烯烃氧烷基化反应: 快速获得α-烷基取代苯乙酮衍生物[J]. 有机化学, 2023, 43(11): 3939-3944.
[5]	王朝彧, 董书达, 朱天阳, 刘玉琴, 武梓涵, 冯若昆. 钴催化的1-萘胺衍生物与α-羰基羧酸的脱羰C(8)-位酰氧基化反应[J]. 有机化学, 2022, 42(6): 1799-1810.
[6]	王银银, 林晓婉, 张飘, 沈美华, 徐华栋, 徐德锋. 基于吡啶和1,3,5-三嗪的PNP钳状配体的设计合成以及在钴催化的末端炔烃半氢化反应中的应用[J]. 有机化学, 2021, 41(8): 3312-3320.
[7]	黄音君, 李金山, 李珅, 马军安. 钴催化2-芳基吲哚氧化去芳构化及与烯酰胺[3+2]环化反应[J]. 有机化学, 2021, 41(10): 4028-4038.
[8]	孙越, 关瑞, 刘兆洪, 王也铭. 铁、钴、镍催化烯烃的硼氢化反应研究进展[J]. 有机化学, 2020, 40(4): 899-912.
[9]	张梦帆, 李瑞鹏, 杨震, 冯若昆. 钴催化双齿导向基辅助的1-萘胺衍生物与醇的区域选择性碳氢键烷氧基化反应[J]. 有机化学, 2020, 40(3): 714-723.
[10]	程彪, 陆鹏, 赵家金, 陆展. 钴催化芳香族烯烃的脱氢硅化反应[J]. 有机化学, 2019, 39(6): 1704-1710.
[11]	孙义明, 丁奇峰, 于杨, 何益得, 黄菲. 钴催化C—H胺化反应的研究进展[J]. 有机化学, 2019, 39(12): 3363-3374.
[12]	王亚琦, 尹强, 郭墩, 韩利民, 孙琪, 洪海龙, 索全伶. 超临界二氧化碳中羰基钴催化的端基炔烃环三聚反应研究[J]. 有机化学, 2019, 39(10): 2898-2905.