Synthesis of α,β-Disubstituted Acrylates via PPh3-Catalyzed Ring-Opening Addition Reaction of Cyclopropenones with Alkyl Bromides at Room Temperature

doi:10.6023/cjoc202505033

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (1): 279-288.DOI: 10.6023/cjoc202505033 Previous Articles Next Articles

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室温下PPh₃催化环丙烯酮与溴代烷烃的开环加成反应合成α,β-二取代丙烯酸酯

徐程^*(), 彭涛, 周梦圆, 刘明琳, 黄晓庆, 王永凤, 刘郑^*(), 殷国栋

湖北师范大学化学化工学院污染物分析与资源化湖北省重点实验室湖北黄石 435002

收稿日期:2025-05-29 修回日期:2025-07-29 发布日期:2025-08-26
基金资助:
国家自然科学基金(22301071); 湖北省中央引导地方科技发展专项(2024CSA097); 湖北省自然科学基金(2023AFB459); 湖北省自然科学基金(2023AFB477); 及大学生创新创业训练计划(202410513026); 及大学生创新创业训练计划(S202410513063)

Synthesis of α,β-Disubstituted Acrylates via PPh₃-Catalyzed Ring-Opening Addition Reaction of Cyclopropenones with Alkyl Bromides at Room Temperature

Cheng Xu^*(), Tao Peng, Mengyuan Zhou, Minglin Liu, Xiaoqing Huang, Yongfeng Wang, Zheng Liu^*(), Guodong Yin

Hubei Key Laboratory of Pollutant Analysis and Reuse Technology, College of Chemistry and Chemical Engineering, Hubei Normal University, Huangshi, Hubei 435002

Received:2025-05-29 Revised:2025-07-29 Published:2025-08-26
Contact: * E-mail: chemxucheng@hbnu.edu.cn; zhengliu0827@hbnu.edu.cn
Supported by:
National Natural Science Foundation of China(22301071); Special Fund Project for Guiding Local Science and Technology Development of Hubei Province by the Central Government(2024CSA097); Natural Science Foundation of Hubei Province(2023AFB459); Natural Science Foundation of Hubei Province(2023AFB477); College Students’ Innovation and Entrepreneurship Training Program(202410513026); College Students’ Innovation and Entrepreneurship Training Program(S202410513063)

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Abstract

A PPh₃-catalyzed ring-opening addition reaction of cyclopropenones with alkyl bromides has been successfully established. This reaction offers a concise and practical approach for the assembly of α,β-disubstituted acrylates with exclusive E-stereoselectivity at room temperature. Mechanistic investigations indicated that both the hydrogen atom on vinyl group and one oxygen atom on ester group of α,β-disubstituted acrylates derive from H₂O in dimethyl sulfoxide (DMSO). Furthermore, a gram-scale experiment and late-stage modification of the products were accomplished, thereby expanding the application potential of this methodology in organic synthesis.

Key words: cyclopropenone, phosphine-catalysis, α,β-disubstituted acrylates, ring-opening addition reaction

Cite this article

Cheng Xu, Tao Peng, Mengyuan Zhou, Minglin Liu, Xiaoqing Huang, Yongfeng Wang, Zheng Liu, Guodong Yin. Synthesis of α,β-Disubstituted Acrylates via PPh₃-Catalyzed Ring-Opening Addition Reaction of Cyclopropenones with Alkyl Bromides at Room Temperature[J]. Chinese Journal of Organic Chemistry, 2026, 46(1): 279-288.

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室温下PPh₃催化环丙烯酮与溴代烷烃的开环加成反应合成α,β-二取代丙烯酸酯

Synthesis of α,β-Disubstituted Acrylates via PPh₃-Catalyzed Ring-Opening Addition Reaction of Cyclopropenones with Alkyl Bromides at Room Temperature

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Entry	Base	Solvent	Temp./℃	Yield^b/%
1	K₂CO₃	CH₃CN	100	76
2	Cs₂CO₃	CH₃CN	100	72
3	CsOAc	CH₃CN	100	64
4	NaOH	CH₃CN	100	42
5	^tBuOK	CH₃CN	100	12
6	Et₃N	CH₃CN	100	11
7	Pyridine	CH₃CN	100	Trace
8	DBU	CH₃CN	100	10
9	K₂CO₃	DMSO	100	82
10	K₂CO₃	DMF	100	73
11	K₂CO₃	Toluene	100	Trace
12	K₂CO₃	Dioxane	100	25
13	K₂CO₃	THF	100	31
14	K₂CO₃	DCM	100	Trace
15	K₂CO₃	Acetone	100	37
16	K₂CO₃	DMSO	60	88
17	K₂CO₃	DMSO	25	91
18^c	K₂CO₃	DMSO	25	Trace
19^d	K₂CO₃	DMSO	25	88
20^e	K₂CO₃	DMSO	25	93

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室温下PPh3催化环丙烯酮与溴代烷烃的开环加成反应合成α,β-二取代丙烯酸酯