Pd-Catalyzed Ring-Opening of gem-Difluorocyclopropanes for the Mono- and Bis-fluoroallylation of 1,3-Dicarbonyls

doi:10.6023/cjoc202312003

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (5): 1630-1640.DOI: 10.6023/cjoc202312003 Previous Articles Next Articles

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钯催化偕二氟环丙烷开环与1,3-二羰基化合物的单/双氟烯丙基化反应

晏宇轩, 陆晚晴, 钱慧俊, 吕雷阳^*(), 李志平^*()

中国人民大学化学系光转换材料与生物光子学实验室北京 100872

收稿日期:2023-12-04 修回日期:2024-01-02 发布日期:2024-01-18
基金资助:
国家自然科学基金(22201300); 国家自然科学基金(22071266); 中央高校基本科研业务费专项资金和中国人民大学科研业务费专项资金(21XNLG04)

Pd-Catalyzed Ring-Opening of gem-Difluorocyclopropanes for the Mono- and Bis-fluoroallylation of 1,3-Dicarbonyls

Yuxuan Yan, Wanqing Lu, Huijun Qian, Leiyang Lv(), Zhiping Li()

Key Laboratory of Advanced Light Conversion Materials and Biophotonics, Department of Chemistry, Renmin University of China, Beijing 100872

Received:2023-12-04 Revised:2024-01-02 Published:2024-01-18
Contact: *E-mail: lvleiyang2020@ruc.edu.cn; zhipingli@ruc.edu.cn
Supported by:
National Natural Science Foundation of China(22201300); National Natural Science Foundation of China(22071266); Fundamental Research Funds for the Central Universities, and the Research Funds of Renmin University of China(21XNLG04)

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Abstract

A palladium-catalyzed ring-opening coupling reaction of gem-difluorocyclopropane with 1,3-dicarbonyl compounds is reported. The bulky and electron-rich biarylphosphine ligand BrettPhos plays a key role. By modifying the reaction conditions and the amount of substrate, the mono- and bis-fluoroallylation reactions of 1,3-dicarbonyl compounds could be realized, respectively. Accordingly, various monofluorinated alkenes were obtained with moderate to excellent yields and branched selectivity. The reaction shows good functional group compatibility and chemoselectivity, and can be applied to the late-stage modification of bioactive molecules.

Key words: Pd catalysis, gem-difluorocyclopropanes, fluoroalkenes, 1,3-dicarbonyls, ring opening reaction

Cite this article

Yuxuan Yan, Wanqing Lu, Huijun Qian, Leiyang Lv, Zhiping Li. Pd-Catalyzed Ring-Opening of gem-Difluorocyclopropanes for the Mono- and Bis-fluoroallylation of 1,3-Dicarbonyls[J]. Chinese Journal of Organic Chemistry, 2024, 44(5): 1630-1640.

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Fig. & Tab. 6

References 23

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Entry	Ligand	Base	Solvent	Yield/%
Entry	Ligand	Base	Solvent	3a	4a
1	IPr•HCl	K₂CO₃	THF
2	IHept•HCl	K₂CO₃	THF
3	RuPhos	K₂CO₃	THF	12	trace
4	X-Phos	K₂CO₃	THF	30	trace
5	XantPhos	K₂CO₃	THF	45	trace
6	BrettPhos	K₂CO₃	THF	89	7
7	BrettPhos	K₃PO₄	THF	87	8
8	BrettPhos	KHCO₃	THF	86	10
9	BrettPhos	KOAc	THF	71	6
10^c	BrettPhos	K₂CO₃	THF	80	19
11	BrettPhos	K₂CO₃	EtOAc	86	9
12	BrettPhos	K₂CO₃	1,4-Dioxane	85	7
13	BrettPhos	K₂CO₃	Toluene	87	8
14	BrettPhos	K₂CO₃	2-MeTHF	87	9
15	BrettPhos		THF
16		K₂CO₃	THF

Entry	Ligand	Base	Solvent	Yield/%
Entry	Ligand	Base	Solvent	3a	4a
1	IPr•HCl	K₂CO₃	THF
2	IHept•HCl	K₂CO₃	THF
3	RuPhos	K₂CO₃	THF	12	trace
4	X-Phos	K₂CO₃	THF	30	trace
5	XantPhos	K₂CO₃	THF	45	trace
6	BrettPhos	K₂CO₃	THF	89	7
7	BrettPhos	K₃PO₄	THF	87	8
8	BrettPhos	KHCO₃	THF	86	10
9	BrettPhos	KOAc	THF	71	6
10^c	BrettPhos	K₂CO₃	THF	80	19
11	BrettPhos	K₂CO₃	EtOAc	86	9
12	BrettPhos	K₂CO₃	1,4-Dioxane	85	7
13	BrettPhos	K₂CO₃	Toluene	87	8
14	BrettPhos	K₂CO₃	2-MeTHF	87	9
15	BrettPhos		THF
16		K₂CO₃	THF

钯催化偕二氟环丙烷开环与1,3-二羰基化合物的单/双氟烯丙基化反应

Pd-Catalyzed Ring-Opening of gem-Difluorocyclopropanes for the Mono- and Bis-fluoroallylation of 1,3-Dicarbonyls

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References 23

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Scope of gem-F₂CPs

Scope of 1,3-dicarbonyls

Scope of gem-F₂CPs

Scope of 1,3-dicarbonyls