Chemoselective Green Synthesis of Cyanoepoxides in Aqueous Solvents

doi:10.6023/cjoc202501019

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (8): 2867-2875.DOI: 10.6023/cjoc202501019 Previous Articles Next Articles

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水介质中氰基环氧化物的化学选择性绿色合成研究

马惠敏^b, 赵宇含^b, 黄业伟^a^,^*(), 孔令斌^a^,^*()

^a 云南农业大学理学院昆明 650201
^b 云南农业大学食品科学技术学院昆明 650201

收稿日期:2025-01-19 修回日期:2025-03-31 发布日期:2025-04-16
基金资助:
云南省基础研究计划(202101AU070247)

Chemoselective Green Synthesis of Cyanoepoxides in Aqueous Solvents

Huimin Ma^b, Yuhan Zhao^b, Yewei Huang^a^,^*(), Lingbin Kong^a^,^*()

^a College of Science, Yunnan Agricultural University, Kunming 650201
^b College of Food Science and Technology, Yunnan Agricultural University, Kunming 650201

Received:2025-01-19 Revised:2025-03-31 Published:2025-04-16
Contact: *E-mail:lichuangyewei100@163.com;konglingbin_ynau@163.com
Supported by:
Yunnan Fundamental Research Projects(202101AU070247)

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Abstract

A chemoselective tandem Knoevenagel-nucleophilic epoxidation reaction using acetonitrile derivatives and aldehyde as starting materials, water as the solvent, and tert-butyl hydroperoxide (TBHP)-1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as the catalytic system to synthesize a series of cyanoepoxides with good yields is developed. This synthetic strategy is environmentally friendly, simple to operate, conducted under mild reaction conditions, and utilizes readily available starting materials with a broad substrate scope. It offers an efficient and green approach for the synthesis of structurally diverse cyanoepoxides.

Key words: cyanoepoxide, nucleophilic epoxidation, chemoselectivity, aqueous solvent

Cite this article

Huimin Ma, Yuhan Zhao, Yewei Huang, Lingbin Kong. Chemoselective Green Synthesis of Cyanoepoxides in Aqueous Solvents[J]. Chinese Journal of Organic Chemistry, 2025, 45(8): 2867-2875.

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Fig. & Tab. 6

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Entry	Solvent	Base	Oxidant	T/℃	Time/h	Yield^b/%
1	MeCN	K₂CO₃	TBHP	r.t.	0.5	58
2	MeOH	K₂CO₃	TBHP	r.t.	0.5	27
3	Acetone	K₂CO₃	TBHP	r.t.	0.5	38
4	H₂O	K₂CO₃	TBHP	r.t.	0.5	52
5	DCE	K₂CO₃	TBHP	r.t.	0.5	N.R.
6	DCM	K₂CO₃	TBHP	r.t.	0.5	Trace
7	CHCl₃	K₂CO₃	TBHP	r.t.	0.5	N.R.
8	DMSO	K₂CO₃	TBHP	r.t.	0.5	Trace
9	THF	K₂CO₃	TBHP	r.t.	0.5	Trace
10	1,4-Dioxane	K₂CO₃	TBHP	r.t.	0.5	Trace
11	H₂O	—	TBHP	r.t.	10	N.R.
12	H₂O	Piperidine	TBHP	r.t.	10	Trace
13	H₂O	Et₃N	TBHP	r.t.	10	Trace
14	H₂O	Cs₂CO₃	TBHP	r.t.	10	Trace
15	H₂O	DBU	TBHP	r.t.	10	78
16	H₂O	DBU	—	r.t.	10	N.R.
17	H₂O	DBU	DTBP	r.t.	10	Trace
18	H₂O	DBU	H₂O₂	r.t.	10	25
19	H₂O	DBU	TBHP	50	0.5	72
20	H₂O	DBU	TBHP	100	0.5	68
21^c	H₂O	DBU	TBHP	r.t.	0.5	73

Entry	Solvent	Base	Oxidant	T/℃	Time/h	Yield^b/%
1	MeCN	K₂CO₃	TBHP	r.t.	0.5	58
2	MeOH	K₂CO₃	TBHP	r.t.	0.5	27
3	Acetone	K₂CO₃	TBHP	r.t.	0.5	38
4	H₂O	K₂CO₃	TBHP	r.t.	0.5	52
5	DCE	K₂CO₃	TBHP	r.t.	0.5	N.R.
6	DCM	K₂CO₃	TBHP	r.t.	0.5	Trace
7	CHCl₃	K₂CO₃	TBHP	r.t.	0.5	N.R.
8	DMSO	K₂CO₃	TBHP	r.t.	0.5	Trace
9	THF	K₂CO₃	TBHP	r.t.	0.5	Trace
10	1,4-Dioxane	K₂CO₃	TBHP	r.t.	0.5	Trace
11	H₂O	—	TBHP	r.t.	10	N.R.
12	H₂O	Piperidine	TBHP	r.t.	10	Trace
13	H₂O	Et₃N	TBHP	r.t.	10	Trace
14	H₂O	Cs₂CO₃	TBHP	r.t.	10	Trace
15	H₂O	DBU	TBHP	r.t.	10	78
16	H₂O	DBU	—	r.t.	10	N.R.
17	H₂O	DBU	DTBP	r.t.	10	Trace
18	H₂O	DBU	H₂O₂	r.t.	10	25
19	H₂O	DBU	TBHP	50	0.5	72
20	H₂O	DBU	TBHP	100	0.5	68
21^c	H₂O	DBU	TBHP	r.t.	0.5	73

水介质中氰基环氧化物的化学选择性绿色合成研究

Chemoselective Green Synthesis of Cyanoepoxides in Aqueous Solvents

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