Synthesis of cis-Alkene with Electron-Withdrawing Groups via Photocatalytic Isomerization

doi:10.6023/cjoc202505010

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (12): 4390-4397.DOI: 10.6023/cjoc202505010 Previous Articles Next Articles

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光催化异构化合成含吸电子取代基顺式烯烃研究

林如海, 毛伟^*(), 涂东怀, 董兴宗, 马辉, 吕剑^*()

西安近代化学研究所氟氮化工新材料全国重点实验室氟氮化工新材料全国重点实验室西安 710065

收稿日期:2025-05-08 修回日期:2025-06-12 发布日期:2025-07-17
通讯作者: 毛伟, 吕剑
基金资助:
国家自然科学基金(22072112); 中央引导地方科技发展资金(2022ZY2-JCYJ-02); 陕西省重点研发计划(2021ZDLGY13-09)

Synthesis of cis-Alkene with Electron-Withdrawing Groups via Photocatalytic Isomerization

Ruhai Lin, Wei Mao^*(), Donghuai Tu, Xingzong Dong, Hui Ma, Jian Lü^*()

State Key Laboratory of Fluorine & Nitrogen Chemical, Xi'an Modern Chemistry Research Institute, Xi'an 710065

Received:2025-05-08 Revised:2025-06-12 Published:2025-07-17
Contact: Wei Mao, Jian Lü
Supported by:
National Natural Science Foundation of China(22072112); Central Guidance for Local Technology Development Funds(2022ZY2-JCYJ-02); Shaanxi Key Research and Development Program(2021ZDLGY13-09)

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Abstract

A method for the photocatalytic isomerization synthesis of cis-olefins containing electron-withdrawing groups is reported. The target cis-alkene was synthesized via photocatalytic isomerization using Ir(ppy)₃ as the photosensitizer and 365 nm UV light as the excitation source. This method features mild reaction conditions, high safety, great selectivity, and broad substrate applicability, providing a valuable strategy for the photocatalytic isomerization synthesis of cis-olefin.

Key words: cis-alkene, photocatalytic isomerization, photosensitizer

Cite this article

Ruhai Lin, Wei Mao, Donghuai Tu, Xingzong Dong, Hui Ma, Jian Lü. Synthesis of cis-Alkene with Electron-Withdrawing Groups via Photocatalytic Isomerization[J]. Chinese Journal of Organic Chemistry, 2025, 45(12): 4390-4397.

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Photosensitizer	λ/nm	Conversion rate/%/%
Riboflavin	365	34.9
Riboflavin	455	33.2
Ir(ppy)₃	365	59.3
Ir(ppy)₃	455	51.8
Eosin Y	365	25.1
Eosin Y	455	20.3
Riboflavin	365	38.7
Riboflavin	455	35.1
Ir(ppy)₃	365	67.2
Ir(ppy)₃	455	60.3
Eosin Y	365	24.9
Eosin Y	455	20.1

Photosensitizer	λ/nm	Conversion rate/%/%
Riboflavin	365	34.9
Riboflavin	455	33.2
Ir(ppy)₃	365	59.3
Ir(ppy)₃	455	51.8
Eosin Y	365	25.1
Eosin Y	455	20.3
Riboflavin	365	38.7
Riboflavin	455	35.1
Ir(ppy)₃	365	67.2
Ir(ppy)₃	455	60.3
Eosin Y	365	24.9
Eosin Y	455	20.1

Compd.	S₀/a.u.	T₁/a.u.	Excited energy barrier/(kJ•mol^－1)
Ir(ppy)₃	－2518.7198827	－2518.6319118	230.96
Riboflavin	－1330.7519889	－1330.72582644	208.76
Thioxanthone	－973.8742644	－973.7974316	201.72
Eosin Y	－11440.2303443	－11440.1591998	186.79

Compd.	S₀/a.u.	T₁/a.u.	Excited energy barrier/(kJ•mol^－1)
Ir(ppy)₃	－2518.7198827	－2518.6319118	230.96
Riboflavin	－1330.7519889	－1330.72582644	208.76
Thioxanthone	－973.8742644	－973.7974316	201.72
Eosin Y	－11440.2303443	－11440.1591998	186.79

Compd.	S₀/a.u.	T₁/a.u.	Excited energy barrier/(kJ•mol^－1)
1a	－646.9630444	－646.867191653	251.66
3a	－761.5343183	－761.444961102	234.61
5a	－514.3580475	－514.283814466	194.90
6a	－2883.3464238	－2883.25594811	237.54
7a	－875.4448938	－875.307474280	360.79
8a	－753.0124878	－752.867234534	381.36
13a	－1059.3803693	－1059.25534541	328.25
14a	－1173.9495601	－1173.82929702	315.75

光催化异构化合成含吸电子取代基顺式烯烃研究

Synthesis of cis-Alkene with Electron-Withdrawing Groups via Photocatalytic Isomerization

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