Electrochemically Promoted Transesterification Reaction of Glycine Derivatives

doi:10.6023/cjoc202406031

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (4): 1360-1368.DOI: 10.6023/cjoc202406031 Previous Articles Next Articles

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电化学促进的甘氨酸衍生物酯交换反应

尤晓琴^†,a, 黄克金^†,b, 庄诗怡^a^,^*(), 刘晨江^b^,^*(), 金伟伟^a^,^*()

a 中国计量大学生命科学学院浙江省特色农产品品质及危害物控制技术重点实验室杭州 310018
b 新疆大学化学学院乌鲁木齐 830017

收稿日期:2024-06-21 修回日期:2024-09-15 发布日期:2024-10-10
作者简介:^† 共同第一作者
基金资助:
国家自然科学基金(22161044); 中国计量大学启动基金(01101-231067)

Electrochemically Promoted Transesterification Reaction of Glycine Derivatives

Xiaoqin You^†,a, Kejin Huang^†,b, Shiyi Zhuang^a(), Chenjiang Liu^b(), Weiwei Jin^a()

a Key Laboratory of Special Agricultural Products Quality and Hazards Controlling Technology of Zhejiang Province, College of Life Sciences, China Jiliang University, Hangzhou 310018
b College of Chemistry, Xinjiang University, Urumqi 830017

Received:2024-06-21 Revised:2024-09-15 Published:2024-10-10
Contact: * E-mail: chemzsy@126.com; pxylcj@126.com; wwjin0722@163.com
About author:^† These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22161044); Scientific Research Foundation of China Jiliang University(01101-231067)

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Abstract

In an undivided cell, using N-phenylglycine ethyl ester as the model substrate, the reaction conditions were optimized. The results showed that the optimal reaction conditions were at room temperature and air condition, using nickel and graphite plate as anode and cathode materials respectively, 2.0 equiv. of NaBr as the electrolyte, ethylene glycol (EG)/dime- thyl-acetamide (DMA) (V∶V=3∶1) as the mixed solvent, and reacting under 6 mA constant current for 3 h. The transesterification reaction could afford various corresponding glycine derivatives up to 88% yield. This mild reaction condition without adding any transition metal, acid or base, was complied with the concept of green chemistry. In addition, 1.32 g of esterification products was successfully synthesized in a gram scale experiment, which also demonstrated the potential value of electrochemical transesterification of glycine derivatives.

Key words: electrochemistry, glycine derivatives, transesterification

Cite this article

Xiaoqin You, Kejin Huang, Shiyi Zhuang, Chenjiang Liu, Weiwei Jin. Electrochemically Promoted Transesterification Reaction of Glycine Derivatives[J]. Chinese Journal of Organic Chemistry, 2025, 45(4): 1360-1368.

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Fig. & Tab. 10

Figure 1. Transesterification reaction

Entry	Electrode	Electrolyte/equiv.	Solvent	Yield^b/%
1	Ni(＋)\|Ni(－)	1.0	EG	75
2	Ni(＋)\|C(－)	1.0	EG	77
3^c	Ni(＋)\|C(－)	1.0	EG	71
4^d	Ni(＋)\|C(－)	1.0	EG	77
5^e	Ni(＋)\|C(－)	1.0	EG	n.r.
6	Ni(＋)\|C(－)	1.5	EG	72
7	Ni(＋)\|C(－)	2.0	EG	92
8	Ni(＋)\|C(－)	2.5	EG	89
9^f	Ni(＋)\|C(－)	1.0	EG	45
10^g	Ni(＋)\|C(－)	1.0	EG	63
11	Ni(＋)\|C(－)	2.0	EG/DMA (V∶V=3∶1)	82
12	Ni(＋)\|C(－)	2.0	EG/CH₃OH (V∶V=3∶1)	Trace
13	Ni(＋)\|C(－)	2.0	EG/EtOH (V∶V=3∶1)	47
14	Ni(＋)\|C(－)	2.0	EG/DMF (V∶V=3∶1)	71
15	Ni(＋)\|C(－)	2.0	EG/DMA (V∶V=1∶1)	55
16	Ni(＋)\|C(－)	2.0	EG/DMA (V∶V=2∶1)	81
17	Ni(＋)\|C(－)	2.0	EG/DMA (V∶V=4∶1)	77

Table 1. Optimization of reaction conditions

Table 2. Substrate scope of glycine esters

Table 3. Substrate scope of alcohols

Figure 2. Gram scale experiment and derivatization

Figure 3. Gram scale experiment equipment

Figure 4. Free radical capture experiments

Figure 5. Cyclic voltammetry curves a Cyclic voltammograms using C disk as work electrode, a Pt disk and Ag/AgCl as counter and reference electrode respectively at 1000 mV/s scan rate. Red line: 3 mL EG, 1 mL DMA, containing 0.4 mmol NaBr; black line: 3 mL EG, 1 mL DMA, containing 0.4 mmol NaBr and 0.2 mmol 1a

Figure 6. Possible reaction mechanism

Figure 7. Transesterification reaction study of glycine esters with alcohols

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电化学促进的甘氨酸衍生物酯交换反应

Electrochemically Promoted Transesterification Reaction of Glycine Derivatives

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