α-Thiocyanation of Enol Acetates and Sodium Thiocyanate under Electrochemical Conditions

doi:10.6023/cjoc202410007

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (1): 189-195.DOI: 10.6023/cjoc202410007 Previous Articles Next Articles

ARTICLES

醋酸烯醇酯与硫氰酸钠电化学条件下α-硫氰化反应

张金鹏^a^,^*(), 钱宇亮^b, 宁梦妍^b, 蔡童钦^b, 苏张竞瑶^b, 于泉^b, 荣良策^b^,^*()

a 徐州医科大学公共卫生学院江苏省生物数据挖掘与医疗健康转化工程研究中心江苏徐州 221004
b 江苏师范大学化学与材料科学学院江苏徐州 221116

收稿日期:2024-10-14 修回日期:2024-12-12 发布日期:2024-12-26
基金资助:
江苏省高校自然科学基础研究计划(18KJA150004); 大学生创新创业训练计划(202410320109Y); 江苏省高校品牌专业及徐州美晗生物科技有限公司资助项目

α-Thiocyanation of Enol Acetates and Sodium Thiocyanate under Electrochemical Conditions

Jinpeng Zhang^a(), Yuliang Qian^b, Mengyan Ning^b, Tongqin Cai^b, Jingyao Su-Zhang^b, Quan Yu^b, Liangce Rong^b()

a Jiangsu Engineering Research Center of Biological Data Mining and Healthcare Transformation, School of Public Health, Xuzhou Medical University, Xuzhou, Jiangsu 221004
b School of Chemistry and Materials Science, Jiangsu Normal University, Xuzhou, Jiangsu 221116

Received:2024-10-14 Revised:2024-12-12 Published:2024-12-26
Contact: *E-mail: lcrong@jsnu.edu.cn; caipj@163.com
Supported by:
Natural Science Foundation of the Jiangsu Higher Education Institutions of China(18KJA150004); Undergraduate Innovation and Entrepreneurship Training Program(202410320109Y); Brand Major of Universities in Jiangsu Province and Xuzhou Meihan Biotechnology Co., Ltd.

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Abstract

An efficient electrochemical α-thiocyanation of enol acetates and sodium thiocyanate was reported in this research. The results showed that enol acetates derived from different types of ketones could be well used in this reaction strategy, and sodium thiocyanate was an excellent thiocyanate source reagent. This approach has the advantages of simple operation, mild reaction conditions and wide range of substrates, which provides an effective process for obtaining α-thiocyanatoones derivatives.

Key words: electrochemistry, enol acetates, α-thiocyanation, sodium thiocyanate

Cite this article

Jinpeng Zhang, Yuliang Qian, Mengyan Ning, Tongqin Cai, Jingyao Su-Zhang, Quan Yu, Liangce Rong. α-Thiocyanation of Enol Acetates and Sodium Thiocyanate under Electrochemical Conditions[J]. Chinese Journal of Organic Chemistry, 2025, 45(1): 189-195.

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Fig. & Tab. 5

References 24

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Entry	Anode/Cathode	Electrolyte	Solvent	Current/mA	Yield^b/%
1	C(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	20	25
2	C(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	5	n.r.
3	C(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	10	n.r.
4	C(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	15	Trace
5	C(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	25	9
6	C(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	30	Trace
7	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	20	82
8	Pt(＋)Ni(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	20	63
9	Pt(＋)Fe(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	20	70
10	RVC(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	20	Trace
11	Pt(＋)Pt(－)	ⁿBu₄NPF₆	V(MeCN)∶V(H₂O)=1∶1	20	29
12	Pt(＋)Pt(－)	LiClO₄	V(MeCN)∶V(H₂O)=1∶1	20	Trace
13	Pt(＋)Pt(－)	TBAB	V(MeCN)∶V(H₂O)=1∶1	20	40
14	Pt(＋)Pt(－)	ⁿBu₄NClO₄	V(MeCN)∶V(H₂O)=1∶1	20	51
15	Pt(＋)Pt(－)	ⁿBu₄NOTf	V(MeCN)∶V(H₂O)=1∶1	20	28
16	Pt(＋)Pt(－)	NaI	V(MeCN)∶V(H₂O)=1∶1	20	n.r.
17	Pt(＋)Pt(－)	ⁿBu₄NBF₄	MeCN	20	n.r.
18	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=2∶1	20	35
19	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=3∶1	20	17
20	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=4∶1	20	Trace
21	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=5∶1	20	Trace
22	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶2	20	30
23	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶3	20	Trace
24	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(EtOH)∶V(H₂O)=1∶1	20	Trace
25	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(Acetone)∶V(H₂O)=1∶1	20	Trace
26	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	20	72^c
27	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	0	n.r

Entry	Anode/Cathode	Electrolyte	Solvent	Current/mA	Yield^b/%
1	C(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	20	25
2	C(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	5	n.r.
3	C(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	10	n.r.
4	C(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	15	Trace
5	C(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	25	9
6	C(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	30	Trace
7	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	20	82
8	Pt(＋)Ni(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	20	63
9	Pt(＋)Fe(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	20	70
10	RVC(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	20	Trace
11	Pt(＋)Pt(－)	ⁿBu₄NPF₆	V(MeCN)∶V(H₂O)=1∶1	20	29
12	Pt(＋)Pt(－)	LiClO₄	V(MeCN)∶V(H₂O)=1∶1	20	Trace
13	Pt(＋)Pt(－)	TBAB	V(MeCN)∶V(H₂O)=1∶1	20	40
14	Pt(＋)Pt(－)	ⁿBu₄NClO₄	V(MeCN)∶V(H₂O)=1∶1	20	51
15	Pt(＋)Pt(－)	ⁿBu₄NOTf	V(MeCN)∶V(H₂O)=1∶1	20	28
16	Pt(＋)Pt(－)	NaI	V(MeCN)∶V(H₂O)=1∶1	20	n.r.
17	Pt(＋)Pt(－)	ⁿBu₄NBF₄	MeCN	20	n.r.
18	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=2∶1	20	35
19	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=3∶1	20	17
20	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=4∶1	20	Trace
21	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=5∶1	20	Trace
22	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶2	20	30
23	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶3	20	Trace
24	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(EtOH)∶V(H₂O)=1∶1	20	Trace
25	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(Acetone)∶V(H₂O)=1∶1	20	Trace
26	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	20	72^c
27	Pt(＋)Pt(－)	ⁿBu₄NBF₄	V(MeCN)∶V(H₂O)=1∶1	0	n.r

醋酸烯醇酯与硫氰酸钠电化学条件下α-硫氰化反应

α-Thiocyanation of Enol Acetates and Sodium Thiocyanate under Electrochemical Conditions

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