Ring Opening Amination of gem-Difluorocyclopropanes with Cyclobutanone Hydrazones

doi:10.6023/cjoc202208031

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (4): 1483-1491.DOI: 10.6023/cjoc202208031 Previous Articles Next Articles

Special Issue: 有机氟化学虚拟合辑

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环丁酮类腙参与的偕二氟环丙烷开环胺化反应

梁志鹏^a, 叶浩^a, 张海滨^b, 姜国民^a^,^*(), 吴新星^a^,^c^,^*()

a 南通大学化学化工学院江苏南通 226019
b 南通职业大学药品与环境工程学院江苏南通 226019
c 江苏浩丰生物科技有限公司江苏南通 226019

收稿日期:2022-08-24 修回日期:2022-11-02 发布日期:2022-12-07
通讯作者: 姜国民, 吴新星
基金资助:
国家自然科学基金(22201145); 南通大学高层次人才科研基金(03083031); 江苏省高校自然科学研究(21KJB150015); 南通大学大型仪器开放基金(KFJN2215)

Ring Opening Amination of gem-Difluorocyclopropanes with Cyclobutanone Hydrazones

Zhipeng Liang^a, Hao Ye^a, Haibin Zhang^b, Guomin Jiang^a(), Xinxing Wu^a^,^c()

a College of Chemistry and Chemical Engineering, Nantong University, Nantong, Jiangsu 226019
b College of Pharmaceutical and Environmental Engineering, Nantong Vocational University, Nantong, Jiangsu 226019
c Jiangsu Haofeng Bio-technology Co., Ltd., Nantong, Jiangsu 226019

Received:2022-08-24 Revised:2022-11-02 Published:2022-12-07
Contact: Guomin Jiang, Xinxing Wu
Supported by:
National Natural Science Foundation of China(22201145); Scientific Research Foundation of High-level Talents of Nantong University(03083031); Universities Natural Science Research Project of Jiangsu Province(21KJB150015); Large Instruments Open Foundation of Nantong University(KFJN2215)

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Abstract

N-Fluoroallyl hydrazones with four-ring structure were effectively synthesized using cyclobutanone hydrazones and gem-difluorocyclopropanes as raw materials through palladium catalyzed ring opening of difluorocyclopropanes and nucleophilic capture process of nitrogen nucleophile. This protocol shows broad substrate scope and good functional group tolerance, which can be applied for gram-scale preparation.

Key words: cyclobutanone hydrazone, gem-difluorocyclopropane, ring opening reaction, monofluoroalkene

Cite this article

Zhipeng Liang, Hao Ye, Haibin Zhang, Guomin Jiang, Xinxing Wu. Ring Opening Amination of gem-Difluorocyclopropanes with Cyclobutanone Hydrazones[J]. Chinese Journal of Organic Chemistry, 2023, 43(4): 1483-1491.

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Fig. & Tab. 7

References 10

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Entry	Ligand	Base	Solvent	Yield^b/%	Z/E^c
1	PPh₃	Cs₂CO₃	Toluene	21	21∶1
2	PPh₃	Cs₂CO₃	MeCN	Trace	—
3	PPh₃	Cs₂CO₃	DME	Trace	—
4	PPh₃	Cs₂CO₃	DCE	30	33∶1
5^d	PPh₃	Cs₂CO₃	THF	37	20∶1
6	PPh₃	Cs₂CO₃	Dioxane	43	28∶1
7	PPh₃	K₂CO₃	Dioxane	40	24∶1
8	PPh₃	^tBuOK	Dioxane	Trace	—
9	PPh₃	^tBuOLi	Dioxane	Trace	—
10	PPh₃	K₃PO₄	Dioxane	51	23∶1
11	PPh₃	NaHCO₃	Dioxane	62	19∶1
12	P(2-furyl)₃	NaHCO₃	Dioxane	Trace	—
13	PCy₃	NaHCO₃	Dioxane	18	23∶1
14	Xphos	NaHCO₃	Dioxane	89	27∶1
15	DPPB	NaHCO₃	Dioxane	28	25∶1
16	Xantphos	NaHCO₃	Dioxane	73	28∶1

Entry	Ligand	Base	Solvent	Yield^b/%	Z/E^c
1	PPh₃	Cs₂CO₃	Toluene	21	21∶1
2	PPh₃	Cs₂CO₃	MeCN	Trace	—
3	PPh₃	Cs₂CO₃	DME	Trace	—
4	PPh₃	Cs₂CO₃	DCE	30	33∶1
5^d	PPh₃	Cs₂CO₃	THF	37	20∶1
6	PPh₃	Cs₂CO₃	Dioxane	43	28∶1
7	PPh₃	K₂CO₃	Dioxane	40	24∶1
8	PPh₃	^tBuOK	Dioxane	Trace	—
9	PPh₃	^tBuOLi	Dioxane	Trace	—
10	PPh₃	K₃PO₄	Dioxane	51	23∶1
11	PPh₃	NaHCO₃	Dioxane	62	19∶1
12	P(2-furyl)₃	NaHCO₃	Dioxane	Trace	—
13	PCy₃	NaHCO₃	Dioxane	18	23∶1
14	Xphos	NaHCO₃	Dioxane	89	27∶1
15	DPPB	NaHCO₃	Dioxane	28	25∶1
16	Xantphos	NaHCO₃	Dioxane	73	28∶1

环丁酮类腙参与的偕二氟环丙烷开环胺化反应

Ring Opening Amination of gem-Difluorocyclopropanes with Cyclobutanone Hydrazones

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