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

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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.

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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

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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

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Fig. & Tab. 7

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