Rhodium-Catalyzed Synthesis of Acyloin Derivatives from Cyclopropenones

doi:10.6023/cjoc202507023

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (2): 486-495.DOI: 10.6023/cjoc202507023 Previous Articles Next Articles

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铑催化由环丙烯酮合成酰偶姻衍生物

任才艺^a^,^†, 董文楠^b^,^†, 刘敬功^c, 杨爽^b, 房新强^a^,^b^,^*()

^a 福州大学化学化工学院福州 350116
^b 中国科学院福建物质结构研究所福州 350100
^c 广州中医药大学第二附属医院广州 510120

收稿日期:2025-07-16 修回日期:2025-09-24 发布日期:2025-11-05
通讯作者: 房新强
作者简介:
^† 共同第一作者
基金资助:
国家自然科学基金(22071242); 国家自然科学基金(21871260)

Rhodium-Catalyzed Synthesis of Acyloin Derivatives from Cyclopropenones

Caiyi Ren^a, Wennan Dong^b, Jinggong Liu^c, Shuang Yang^b, Xinqiang Fang^a^,^b^,^*()

^a College of Chemistry, Fuzhou University, Fuzhou 350116
^b Fujian Institute of Research on the Structure of Matter, Chinese Academy of Science, Fuzhou 350100
^c The Second Affiliated Hospital of Guangzhou University of Chinese Medicine, Guangzhou 510120

Received:2025-07-16 Revised:2025-09-24 Published:2025-11-05
Contact: Xinqiang Fang
About author:
^† These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(22071242); National Natural Science Foundation of China(21871260)

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Abstract

Cyclopropenones have been extensively utilized in catalytic ring-opening and ring-expansion reactions for the synthesis of unsaturated carbonyl compounds. The first rhodium-catalyzed ring-opening reaction of aryl-/alkyl-substituted cyclopropenones is accomplished, successfully affording acyloin derivatives. This transformation represents a novel reaction pattern involving cyclopropenones. The resulting acyloin products constitute important building blocks in organic synthesis and serve as fundamental structural frameworks in numerous natural products.

Key words: cyclopropenone, rhodium catalysis, acyloin, ring-opening reaction

Cite this article

Caiyi Ren, Wennan Dong, Jinggong Liu, Shuang Yang, Xinqiang Fang. Rhodium-Catalyzed Synthesis of Acyloin Derivatives from Cyclopropenones[J]. Chinese Journal of Organic Chemistry, 2026, 46(2): 486-495.

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References 11

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Entry	Cat.	Hydrogen donor/base	HCO₂H/equiv.	Solven	Additive	Temp./℃	Time/h	Yield^b/% of 2a	rr^c (2a∶3a)
1	A	HCO₂H/Et₃N	60	—	—	20	9.5	Trace	—
2	B	HCO₂H/Et₃N	60	—	—	20	19	51	6∶1
3	C	HCO₂H/Et₃N	60	—	—	30	11	Trace	—
4	D	HCO₂H/Et₃N	60	—	—	30	11	Trace	—
5	E	HCO₂H/Et₃N	60	—	—	30	11	Trace	—
6	B	HCO₂H/TMEDA	60	—	—	30	12	11	3∶1
7	B	HCO₂H/DABCO	60	—	—	30	13	Trace	—
8	B	HCO₂H/^tBuOK	60	—	—	30	12	Trace	—
9	B	HCO₂H/Cs₂CO₃	60	—	—	30	12	Trace	—
10	B	HCO₂H/Et₃N	120	—	—	30	24	32	5∶1
11	B	HCO₂H/Et₃N	30	—	—	30	24	66	6∶1
12	B	HCO₂H/Et₃N	30	THF	—	30	24	29	1∶1
13	B	HCO₂H/Et₃N	30	MeOH	—	30	24	Trace	—
14	B	HCO₂H/Et₃N	30	MeCN	—	30	24	70	4∶1
15	B	HCO₂H/Et₃N	30	CH₂Cl₂	—	30	24	72	6∶1
16	B	HCO₂H/Et₃N	30	CHCl₃	—	30	24	52	4∶1
17	B	HCO₂H/Et₃N	30	CH₂ClCH₂Cl	—	30	24	70	5∶1
18	B	HCO₂H/Et₃N	30	Acetone	—	30	24	Trace	—
19	B	HCO₂H/Et₃N	30	Toluene	—	30	24	71	4∶1
20	B	HCO₂H/Et₃N	30	CH₂Cl₂	Zn(OTf)₂	30	24	45	5∶1
21	B	HCO₂H/Et₃N	30	CH₂Cl₂	Mg(OTf)₂	30	24	52	5∶1
22	B	HCO₂H/Et₃N	30	CH₂Cl₂	MgBr₂•Et₂O	30	24	54	8∶1
23	—	HCO₂H/Et₃N	30	CH₂Cl₂	—	30	24	Trace	—

Entry	Cat.	Hydrogen donor/base	HCO₂H/equiv.	Solven	Additive	Temp./℃	Time/h	Yield^b/% of 2a	rr^c (2a∶3a)
1	A	HCO₂H/Et₃N	60	—	—	20	9.5	Trace	—
2	B	HCO₂H/Et₃N	60	—	—	20	19	51	6∶1
3	C	HCO₂H/Et₃N	60	—	—	30	11	Trace	—
4	D	HCO₂H/Et₃N	60	—	—	30	11	Trace	—
5	E	HCO₂H/Et₃N	60	—	—	30	11	Trace	—
6	B	HCO₂H/TMEDA	60	—	—	30	12	11	3∶1
7	B	HCO₂H/DABCO	60	—	—	30	13	Trace	—
8	B	HCO₂H/^tBuOK	60	—	—	30	12	Trace	—
9	B	HCO₂H/Cs₂CO₃	60	—	—	30	12	Trace	—
10	B	HCO₂H/Et₃N	120	—	—	30	24	32	5∶1
11	B	HCO₂H/Et₃N	30	—	—	30	24	66	6∶1
12	B	HCO₂H/Et₃N	30	THF	—	30	24	29	1∶1
13	B	HCO₂H/Et₃N	30	MeOH	—	30	24	Trace	—
14	B	HCO₂H/Et₃N	30	MeCN	—	30	24	70	4∶1
15	B	HCO₂H/Et₃N	30	CH₂Cl₂	—	30	24	72	6∶1
16	B	HCO₂H/Et₃N	30	CHCl₃	—	30	24	52	4∶1
17	B	HCO₂H/Et₃N	30	CH₂ClCH₂Cl	—	30	24	70	5∶1
18	B	HCO₂H/Et₃N	30	Acetone	—	30	24	Trace	—
19	B	HCO₂H/Et₃N	30	Toluene	—	30	24	71	4∶1
20	B	HCO₂H/Et₃N	30	CH₂Cl₂	Zn(OTf)₂	30	24	45	5∶1
21	B	HCO₂H/Et₃N	30	CH₂Cl₂	Mg(OTf)₂	30	24	52	5∶1
22	B	HCO₂H/Et₃N	30	CH₂Cl₂	MgBr₂•Et₂O	30	24	54	8∶1
23	—	HCO₂H/Et₃N	30	CH₂Cl₂	—	30	24	Trace	—

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铑催化由环丙烯酮合成酰偶姻衍生物

Rhodium-Catalyzed Synthesis of Acyloin Derivatives from Cyclopropenones

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