Photoredox Catalysis for the Coupling Reaction of Nitrones with Aromatic Tertiary Amines

doi:10.6023/A19040150

Acta Chimica Sinica ›› 2019, Vol. 77 ›› Issue (9): 850-855.DOI: 10.6023/A19040150 Previous Articles Next Articles

Special Issue: 有机自由基化学

Communication

光催化氧化还原体系中硝酮与芳香叔胺的自由基偶联反应

刘玉成, 郑啸^*(), 黄培强^*()

厦门大学化学化工学院化学系福建省化学生物学重点实验室厦门 361005

投稿日期:2019-04-30 发布日期:2019-05-22
通讯作者: 郑啸,黄培强 E-mail:zxiao@xmu.edu.cn;pqhuang@xmu.edu.cn
基金资助:
项目受国家重点研发计划(No.2017YFA0207302);国家自然科学基金(Nos.21672175);国家自然科学基金(91856110);国家自然科学基金(21332007);国家自然科学基金(21472153);教育部长江学者和创新团队发展计划资助

Photoredox Catalysis for the Coupling Reaction of Nitrones with Aromatic Tertiary Amines

Liu, Yu-Cheng, Zheng, Xiao^*(), Huang, Pei-Qiang^*()

Department of Chemistry, Fujian Provincial Key Laboratory of Chemical Biology, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China

Received:2019-04-30 Published:2019-05-22
Contact: Zheng, Xiao,Huang, Pei-Qiang E-mail:zxiao@xmu.edu.cn;pqhuang@xmu.edu.cn
Supported by:
Project supported by the National Key Research and Development Program of China(No.2017YFA0207302);the National Natural Science Foundation of China(Nos.21672175);the National Natural Science Foundation of China(91856110);the National Natural Science Foundation of China(21332007);the National Natural Science Foundation of China(21472153);the Program for Changjiang Scholars and Innovative Research Team in University (PCSIRT) of Ministry of Education, China

1. Photoredox Catalysis for the Coupling Reaction of Nitrones with Aromatic Tertiary Amines.PDF(3881KB)

Abstract

Carbon-carbon bond formation at α-amino carbon based on α-aminoalkyl radicals is an essential transformation in the synthesis of nitrogen-containing compounds. Recently, some novel photoredox catalytic protocols for this goal have been developed, in which α-aminoalkyl radicals were generated from a sequential oxidation/α-deprotonation of aromatic tertiary amines. Inspired by these studies and based on our previous works, we have developed the cross-coupling reaction of nitrones with aromatic tertiary amines via visible light photoredox catalysis. This method features a radical addition of α-aminoalkyl radicals to nitrones with advantages of simple operation, mild conditions, atom economy, a broad scope of nitrone substrates; and allows for an easy access to β-amino hydroxylamines, which could be readily converted into vicinal diamines. Compared with the UV-excited organophotosensitizer-promoted coupling reaction of nitrones with tertiary amines, visible light is a more safe and convenient light source, the photo-excited electron transfer (PET) by 1 mol% of Ir-photocatalyst is more efficient. In addition, nitrones exclusively server as excellent radical acceptors thus with a broader range of structures. A general procedure of this coupling reaction is as follows: To a 25 mL Schlenk tube equipped with a magnetic stir bar were added a nitrone (0.30 mmol), a tertiary amine (0.90 mmol), Ir(ppy)₂(dtbbpy)PF₆ (0.003 mmol, 1.0 mol%) and K₂HPO₄ (0.06 mmol, 20 mol%). After being evacuated and backfilled with argon for three times, DMSO (3 mL) was added to the tube. Then the tube was placed approximately 7 cm away from a 12 W blue LEDs, and the reaction mixture was stirred at r.t. under an argon atmosphere for 24 h. The reaction was quenched with saturated aqueous NaHCO₃ (25 mL), and the mixture was extracted with dichloromethane (DCM, 20 mL×3). The combined organic layers were washed with brine, dried over anhydrous Na₂SO₄, filtered and concentrated under reduced pressure. The residue was purified by flash column chromatography on silica gel to afford the desired cross-coupling product β-amino hydroxylamine.

Key words: α-aminoalkyl radicals, photoredox catalysis, coupling reaction, aromatic tertiary amine, nitrone

Cite this article

Liu, Yu-Cheng, Zheng, Xiao, Huang, Pei-Qiang. Photoredox Catalysis for the Coupling Reaction of Nitrones with Aromatic Tertiary Amines[J]. Acta Chimica Sinica, 2019, 77(9): 850-855.

Export EndNote|Reference Manager|ProCite|BibTeX|RefWorks

share this article

Fig. & Tab. 7

Scheme 1. The design of cross-coupling of nitrones with aromatic tertiary amines via visible light photoredox catalysis

Entry	Variation from standard condition	Yield/%
1	Ru(bpy)₃(PF₆)₂/Cs₂CO₃	14
2		84
3	No Photocatalyst	0
4	No LEDs	0
5	No K₂HPO₄	0

Table 1. Control experiments

Table 2. Cross-coupling of nitrones with N,N-dimethylaniline 2a

Table 3. Cross-coupling of nitrone 1a with aromatic tertiary amines

Scheme 2. The trapping experiment of α-aminoalkyl radical

Scheme 3. Recovery of tertiary amine at the end of the reaction

Scheme 4. The proposed mechanism

References 14

[1]	(a) Renaud, P.; Giraud, L. Synthesis 1996,913 doi: 10.1021/acs.accounts.6b00251
	(b) Hart, D. in Radicals in Organic Synthesis; Renaud, P.; Sibi, M. P. Eds. Weinheim, Germany: Wiley-VCH, 2001, Vol. 2: pp 279; doi: 10.1021/acs.accounts.6b00251
	(c) Aurrecoechea, J. M.; Suero, R . Arkivoc. 2004, part xiv, 10, at www.arkat-usa.org; doi: 10.1021/acs.accounts.6b00251
	(d) Nakajima, K.; Miyake, Y.; Nishibayashi, Y . Acc. Chem. Res.. 2016, 49, 1946. doi: 10.1021/acs.accounts.6b00251
[2]	For some selected reviews on visible light photocatalysis, see: (a) Prier, C. K.; Rankic, D. A.; MacMillan, D. W. C. Chem. Rev. 2013, 113, 5322 doi: 10.1021/cr300503r
	(b) Skubi, K. L.; Blum, T. R.; Yoon, T. P. Chem. Rev. 2016, 116, 10035; doi: 10.1021/cr300503r
	(c) Fagnoni, M.; Dondi, D.; Ravelli, D.; Albini, A . Chem. Rev. 2007, 107, 2725; doi: 10.1021/cr300503r
	(d) Beatty, J. B.; Stephenson, C. R. J . Acc. Chem. Res. 2015, 48, 1474; doi: 10.1021/cr300503r
	(e) Tellis, J. C.; Kelly, C. B.; Primer, D. N.; Jouffroy, M.; Patel, N. R.;Molander, G. A.; . Acc. Chem. Res.. 2016, 49, 1429; doi: 10.1021/cr300503r
	(f) Ghosh, L.; Marzo, L.; Das, A.; Shaikh, R.; König, B . Acc. Chem. Res. 2016, 49, 1566; doi: 10.1021/cr300503r
	(g) Chen, J.-R.; Hu, X.-Q.; Lu, L.-Q.; Xiao, W.-J . Acc. Chem. Res. 2016, 49, 1911; doi: 10.1021/cr300503r
	(h) Arora, A.; Weaver, J. D . Acc. Chem. Res. 2016, 49, 2273; doi: 10.1021/cr300503r
	(i) Li, W.; Zheng, X.-Y.; Zeng, J.-G.; Cheng, P . Chin. J. Org. Chem.. 2017, 37, 1 (in Chinese); doi: 10.1021/cr300503r
	(刘薇, 郑昕宇, 曾建国, 程辟, 有机化学, Chin. J. Org. Chem. 2017, 37, 1; doi: 10.1021/cr300503r
	(j) Wang, D.-H.; Zhang, L.; Luo, S.-Z . Acta Chim. Sinica. 2017, 75, 22 (in Chinese); doi: 10.1021/cr300503r
	(王德红, 张龙, 罗三中, 化学学报, 2017, 75, 22); doi: 10.1021/cr300503r
	(k) Song, H.; Liu, X.-Y.; Qin, Y . Acta Chim. Sinica. 2017, 75, 1137 (in Chinese); doi: 10.1021/cr300503r
	(宋颢, 刘小宇, 秦勇, 化学学报, 2017, 75, 1137); doi: 10.1021/cr300503r
	(l) Cheng, X.-K.; Hu, X.-G.; Lu, Z . Chin. J. Org. Chem.. 2017, 37, 251 (in Chinese); doi: 10.1021/cr300503r
	(程骁恺, 胡新根, 陆展, 化学学报, 2017, 37, 251; doi: 10.1021/cr300503r
	(m) Wu, J.; Li, J.-W.; Li, H.; Zhu, C.-Y . Chin. J. Org. Chem.. 2017, 37, 2203 (in Chinese); doi: 10.1021/cr300503r
	(吴江, 李嘉雯, 李昊, 朱纯银, 有机化学, 2017, 37, 2203); doi: 10.1021/cr300503r
	(n) Liu, Y.-H.; Dong, W . Chin. J. Chem.. 2017, 35, 1491; doi: 10.1021/cr300503r
	(o) Ruan, L.-H.; Dong, Z.-C.; Chen, C.-X.; Wu, S.; Sun, J . Chin. J. Org. Chem.. 2017, 37, 2544 (in Chinese); doi: 10.1021/cr300503r
	(阮利衡, 董振诚, 陈春欣, 吴爽, 孙京, 有机化学, 2017, 37, 2544); doi: 10.1021/cr300503r
	(p) Yi, H.; Zhang, G.-T.; Wang, H.-M.; Huang, Z.-Y.; Wang, J.; Singh, A. K.; Lei, A.-W . Chem. Rev.. 2017, 117, 9016; doi: 10.1021/cr300503r
	(q) Ye, H.; Xiao, C.; Lu, L.-Q . Chin. J. Org. Chem.. 2018, 38, 1897 (in Chinese); doi: 10.1021/cr300503r
	(叶辉, 肖聪, 陆良秋, 有机化学, 2018, 38, 1897); doi: 10.1021/cr300503r
	(r) Xu, W.-X.; Dai, X.-Q.; Xu, H.-J.; Weng, J.-Q . Chin. J. Org. Chem.. 2018, 38, 2807 (in Chinese); doi: 10.1021/cr300503r
	(徐雯秀, 戴小强, 徐涵靖, 翁建全, 有机化学, 2018, 38, 2807). doi: 10.1021/cr300503r
[3]	(a) McNally, A.; Prier, C. K.; MacMillan, D. W. C. Science 2011, 334, 1114 doi: 10.1126/science.1213920
	(b) Prier, C. K.; MacMillan, D. W. C. Chem. Sci. 2014, 5, 4173. doi: 10.1126/science.1213920
[4]	(a) Miyake, Y.; Nakajima, K.; Nishibayashi, Y. J. Am. Chem. Soc. 2012, 134, 3338 doi: 10.1021/ja211770y
	(b) Kohls, P.; Jadhav, K.; Pandey, G.; Reiser, O . Org. Lett., 2012, 14, 672; doi: 10.1021/ja211770y
	(c) Espelt, L. R.; Wiensch, E. R.; Yoon, T. P . J. Org. Chem. 2013, 78, 4107; doi: 10.1021/ja211770y
	(d) Lin, S.-X.; Sun, G.-J.; Kang, Q . Chem. Commun.. 2017, 53, 7665. doi: 10.1021/ja211770y
[5]	Miyake, Y.; Nakajima, K.; Nishibayashi, Y. Chem. Eur. J. 2012, 18, 16473. doi: 10.1002/chem.201203066
[6]	(a) Uraguchi, D.; Kinoshita, N.; Kizu, T.; Ooi, T. J. Am. Chem. Soc. 2015, 137, 13768 doi: 10.1021/jacs.5b09329
	(b) Fava, E.; Millet, A.; Nakajima, M.; Loescher, S.; Rueping, M. Angew. Chem. Int. Ed. 2016, 55, 6776. doi: 10.1021/jacs.5b09329
[7]	(a) Wang, C.-Y.; Qin, J.; Shen, X.-D.; Riedel, R.; Harms, K.; Meggers, E. Angew. Chem. Int. Ed. 2016, 55, 685 doi: 10.1002/anie.201509524
	(b) Li, W.-P.; Duan, Y.-Q.; Zhang, M.-L.; Cheng, J.; Zhu, C.-J . Chem. Commun. 2016, 52, 7596. doi: 10.1002/anie.201509524
[8]	Zhou, Q.-Q.; Liu, D.; Xiao, W.-J.; Lu, L.-Q . Acta Chim. Sinica 2017, 75, 110 (in Chinese) doi: 10.6023/A16080414
	( 周泉泉, 刘丹, 肖文精, 陆良秋, 化学学报 , 2017, 75, 110). doi: 10.6023/A16080414
[9]	Itoh, K.; Kato, R.; Kinugawa, D.; Kamiya, H.; Kudo, R.; Hasegawa, M.; Fujii, H.; Suga, H. Org. Biomol. Chem. 2015, 13, 8919. doi: 10.1039/C5OB01277E
[10]	(a) Rau, H . Chem. Rev.. 1983, 83, 535; doi: 10.1021/cr00057a003
	(b) Inoue, Y . Chem. Rev.. 1992, 92, 741; doi: 10.1021/cr00057a003
	(c) Peters, K. S . Adv. Photochem.. 2002, 27, 51; doi: 10.1021/cr00057a003
	(d) Fagnoni, M.; Dondi, D.; Ravelli, D.; Albini, A . Chem. Rev.. 2007, 107, 2725; doi: 10.1021/cr00057a003
	(e) Hoffmann, N . Chem. Rev.. 2008, 108, 1052; doi: 10.1021/cr00057a003
	(f) Bach, T.; Hehn, J. P . Angew. Chem., Int. Ed.. 2011, 50, 1000. doi: 10.1021/cr00057a003
[11]	(a) Szostak, M.; Fazakerley, N. J.; Parmar, D.; Procter, D. J. Chem. Rev. 2014, 114, 5959 doi: 10.1021/cr400685r
	(b) Zheng, X.; Huang, P.-Q. Prog. Chem. 2018, 30, 528. doi: 10.1021/cr400685r
[12]	Ye, C.-X.; Melcamu, Y. Y.; Li, H.-H.; Cheng, J.-T.; Zhang, T.-T.; Ruan, Y.-P.; Zheng, X.; Lu, X.; Huang, P.-Q . Nat. Commun. 2018, 9, 410. doi: 10.1038/s41467-017-02698-4
[13]	Zhong, Y.-W.; Xu, M.-H.; Lin, G.-Q . Org. Lett. 2004, 6, 3953. doi: 10.1021/ol048444d
[14]	For reviews on vicinal diamines, see: (a) Lucet, D.; Gall, T. L.; Mioskowski, C. Angew. Chem. Int. Ed. 1998, 37, 2580 doi: 10.1002/(ISSN)1521-3773
	(b) Visa, A.; Pradilla, R. F.; Garcίa, A.; Flores, A . Chem. Rev. 2005, 105, 3167; doi: 10.1002/(ISSN)1521-3773
	(c) Kotti, S. R. S. S.; Timmons, C.; Li, G . Chem. Biol. Drug. Des.. 2006, 67, 101; doi: 10.1002/(ISSN)1521-3773
	(d) Cardona, F.; Goti, A . Nat. Chem.. 2009, 1, 269.; doi: 10.1002/(ISSN)1521-3773
	(e) Grygorenko, O. O.; Radchenko, D. S.; Volochnyuk, D. M.; Tolmachev, A. A.; Komarov, I. V . Chem. Rev. 2011, 111, 5506; doi: 10.1002/(ISSN)1521-3773
	(f) Zhu, Y.-G.; Cornwall, R. G.; Du, H.-F.; Zhao, B.-G.; Shi, Y . Acc. Chem. Res.. 2014, 47, 3665. doi: 10.1002/(ISSN)1521-3773

[1]	Zhang, Zhen, Gong, Li, Zhou, Xiao-Yu, Yan, Si-Shun, Li, Jing, Yu, Da-Gang. Radical-Type Difunctionalization of Alkenes with CO₂ [J]. Acta Chimica Sinica, 2019, 77(9): 783-793.
[2]	Zhang, Hong-Hao, Yu, Shouyun. Advances on Transition Metals and Photoredox Cooperatively Catalyzed Allylic Substitutions [J]. Acta Chimica Sinica, 2019, 77(9): 832-840.
[3]	Cheng, Zhongming, Chen, Pinhong, Liu, Guosheng. Enantioselective Cyanation of Remote C—H Bonds via Cooperative Photoredox and Copper Catalysis [J]. Acta Chimica Sinica, 2019, 77(9): 856-860.
[4]	Li Yue, Jiang Yuchen, Jiang Pingping, Du Shengyu, Jiang Jiusheng, Leng Yan. Molybdenum Nanocarbides Encapsulated in Porous Carbon Spheres for Solvent-free Benzyl Amine Oxidative Coupling Reactions [J]. Acta Chim. Sinica, 2019, 77(1): 66-71.
[5]	Gu Zhengyang, Ji Shunjun. Recent Advances in Cobalt Catalyzed Isocyanide Coupling Reactions [J]. Acta Chim. Sinica, 2018, 76(5): 347-356.
[6]	Shi Minglin, Zhan Gu, Du Wei, Chen Yingchun. Direct Asymmetric Aza-Vinylogous Mannich Reaction of Nitrones from Isatins and Ketimines [J]. Acta Chim. Sinica, 2017, 75(10): 998-1002.
[7]	Rong Jian, Ni Chuanfa, Wang Yunze, Kuang Cuiwen, Gu Yucheng, Hu Jinbo. Radical Fluoroalkylation of Aryl Alkenes with Fluorinated Sulfones by Visible-Light Photoredox Catalysis [J]. Acta Chimica Sinica, 2017, 75(1): 105-109.
[8]	Wang Dehong, Zhang Long, Luo Sanzhong. Photo-induced Catalytic Asymmetric Free Radical Reactions [J]. Acta Chim. Sinica, 2017, 75(1): 22-33.
[9]	Wu Zijun, Wang Jian. Decarboxylative 1,6-Conjugate Addition of α-Keto Acids with para-Quinone Methides Enabled by Photoredox Catalysis [J]. Acta Chim. Sinica, 2017, 75(1): 74-79.
[10]	Zhou Quanquan, Liu Dan, Xiao Wenjing, Lu Liangqiu. Visible-Light Photoredox Catalytic α-Cyanation Reactions of Tertiary Amines [J]. Acta Chim. Sinica, 2017, 75(1): 110-114.
[11]	Tang Haoming, Huo Xiaohong, Meng Qinghua, Zhang Wanbin. Palladium-Catalyzed Allylic C—H Functionalization: The Development of New Catalytic Systems [J]. Acta Chim. Sinica, 2016, 74(3): 219-233.
[12]	Yan Zhuojun, Yuan Ye, Liu Jia, Li Qin, Nguyen Nam-Trung, Zhang Daming, Tian Yuyang, Zhu Guangshan. Targeted Syntheses of Charged Porous Aromatic Frameworks for Iodine Enrichment and Release [J]. Acta Chim. Sinica, 2016, 74(1): 67-73.
[13]	Xiao Yulan, Pan Qiang, Zhang Xingang. Nickel-Catalyzed Cross-Coupling of gem-Difluoropropargyl Bromide with Aryl Boronic Acids [J]. Acta Chim. Sinica, 2015, 73(5): 383-387.
[14]	Tan Fen, Xiao Wenjing. Visible-Light Photoredox Catalysis in Natural Products Synthesis [J]. Acta Chim. Sinica, 2015, 73(2): 85-89.
[15]	Zhang Tingting, Wang Haitao, Ma Heping, Sun Fuxing, Cui Xiaoqiang, Zhu Guangshan. Construction and Characterization of Pyrene-alkyne Based Porous Frameworks [J]. Acta Chimica Sinica, 2013, 71(12): 1598-1602.

光催化氧化还原体系中硝酮与芳香叔胺的自由基偶联反应

Photoredox Catalysis for the Coupling Reaction of Nitrones with Aromatic Tertiary Amines

RichHTML

PDF

Supporting Info.

Knowledge

Abstract

Cite this article

share this article

Fig. & Tab. 7

References 14

Related Articles 15

Recommended Articles

Metrics

Comments