Amide-Oxazoline-Directed Copper-Catalyzed C—H Acyloxylation of [2.2]Paracyclophanes

doi:10.6023/cjoc202602012

Chinese Journal of Organic Chemistry ›› 2026, Vol. 46 ›› Issue (8): 3147-3157.DOI: 10.6023/cjoc202602012 Previous Articles Next Articles

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酰胺噁唑啉导向的铜催化[2.2]对环芳烷直接C—H酰氧基化反应

韩银松, 王东炜, 肖佳怡, 冯若昆^*()

绍兴大学化学化工学院浙江绍兴 312000

收稿日期:2026-02-10 修回日期:2026-04-05 发布日期:2026-05-18
通讯作者: 冯若昆
基金资助:
浙江省自然科学基金(LQ15B020002); 绍兴市重点科技创新团队(202034); 国家级大学生创新创业训练计划(202410349028)

Amide-Oxazoline-Directed Copper-Catalyzed C—H Acyloxylation of [2.2]Paracyclophanes

Yinsong Han, Dongwei Wang, Jiayi Xiao, Ruokun Feng^*()

College of Chemistry and Chemical Engineering, Shaoxing University, Shaoxing, Zhejiang 312000

Received:2026-02-10 Revised:2026-04-05 Published:2026-05-18
Contact: Ruokun Feng
Supported by:
Zhejiang Provincial Natural Science Foundation(LQ15B020002); Shaoxing Key Science and Technology Innovation Team Project(202034); National College Students’ Innovation and Entrepreneurship Training Program(202410349028)

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Abstract

A copper-catalyzed direct C—H acyloxylation of [2.2]paracyclophanes utilizing an oxazoline amide directing group has been developed. A range of carboxylic acid substrates, including aromatic, alkenyl, and alkyl carboxylic acids, are tolerated, delivering the corresponding acyloxylated products in moderate to good yields. Gram-scale reactions and subsequent hydrolysis experiments further demonstrate the synthetic utility of this method. This work provides an efficient and convenient strategy for the selective functionalization of [2.2]paracyclophanes, highlighting its potential for practical applications.

Key words: copper catalysis, amide oxazoline directing, C—H acyloxylation, [2.2]paracyclophanes

Cite this article

Yinsong Han, Dongwei Wang, Jiayi Xiao, Ruokun Feng. Amide-Oxazoline-Directed Copper-Catalyzed C—H Acyloxylation of [2.2]Paracyclophanes[J]. Chinese Journal of Organic Chemistry, 2026, 46(8): 3147-3157.

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Fig. & Tab. 5

References 15

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Entry	Cu	Oxidant	Solvent	Temp./℃	Time/h	Yield^b/%
1	CuBr₂	Ag₂CO₃	V(Toluene)∶V(DMA)=3∶1	130	12	51
2	CuCl₂	Ag₂CO₃	V(Toluene)∶V(DMF)=3∶1	130	12	54
3	Cu(OAc)₂	Ag₂CO₃	V(Toluene)∶V(DMA)=3∶1	130	12	37
4	CuI	Ag₂CO₃	V(Toluene)∶V(DMA)=3∶1	130	12	41
5	CuCl	Ag₂CO₃	V(Toluene)∶V(DMA)=3∶1	130	12	61
6	CuBr	Ag₂CO₃	V(Toluene)∶V(DMA)=3∶1	130	12	58
7	—	Ag₂CO₃	V(Toluene)∶V(DMA)=3∶1	130	12	NR^c
8	CuCl	Ag₂SO₄	V(Toluene)∶V(DMA)=3∶1	130	12	NR
9	CuCl	AgOAc	V(Toluene)∶V(DMA)=3∶1	130	12	NR
10	CuCl	O₂	V(Toluene)∶V(DMA)=3∶1	130	12	NR
11	CuCl	Ag₂CO₃	V(Toluene)∶V(DMA)=3∶1	130	12	42
12	CuCl	—	V(Toluene)∶V(DMA)=3∶1	130	12	NR
13	CuCl	Ag₂CO₃	V(Toluene)∶V(DMA)=1∶1	130	12	43
14	CuCl	Ag₂CO₃	V(Toluene)∶V(DMA)=1∶2	130	12	40
15	CuCl	Ag₂CO₃	V(Toluene)∶V(DMA)=1∶3	130	12	34
16^d	CuCl	Ag₂CO₃	Toluene	130	12	47
17	CuCl	Ag₂CO₃	V(Toluene)∶V(DMSO)=3∶1	130	12	67
18	CuCl	Ag₂CO₃	V(Toluene)∶V(DMF)=3∶1	130	12	50
19	CuCl	Ag₂CO₃	V(Toluene)∶V(DMF)=3∶1	110	12	32
20	CuCl	Ag₂CO₃	V(Toluene)∶V(DMF)=3∶1	150	12	39
21	CuCl	Ag₂CO₃	V(Toluene)∶V(DMF)=3∶1	130	8	58
22	CuCl	Ag₂CO₃	V(Toluene)∶V(DMF)=3∶1	130	16	66
23^e	CuCl	Ag₂CO₃	V(Toluene)∶V(DMF)=3∶1	130	12	25

Entry	Cu	Oxidant	Solvent	Temp./℃	Time/h	Yield^b/%
1	CuBr₂	Ag₂CO₃	V(Toluene)∶V(DMA)=3∶1	130	12	51
2	CuCl₂	Ag₂CO₃	V(Toluene)∶V(DMF)=3∶1	130	12	54
3	Cu(OAc)₂	Ag₂CO₃	V(Toluene)∶V(DMA)=3∶1	130	12	37
4	CuI	Ag₂CO₃	V(Toluene)∶V(DMA)=3∶1	130	12	41
5	CuCl	Ag₂CO₃	V(Toluene)∶V(DMA)=3∶1	130	12	61
6	CuBr	Ag₂CO₃	V(Toluene)∶V(DMA)=3∶1	130	12	58
7	—	Ag₂CO₃	V(Toluene)∶V(DMA)=3∶1	130	12	NR^c
8	CuCl	Ag₂SO₄	V(Toluene)∶V(DMA)=3∶1	130	12	NR
9	CuCl	AgOAc	V(Toluene)∶V(DMA)=3∶1	130	12	NR
10	CuCl	O₂	V(Toluene)∶V(DMA)=3∶1	130	12	NR
11	CuCl	Ag₂CO₃	V(Toluene)∶V(DMA)=3∶1	130	12	42
12	CuCl	—	V(Toluene)∶V(DMA)=3∶1	130	12	NR
13	CuCl	Ag₂CO₃	V(Toluene)∶V(DMA)=1∶1	130	12	43
14	CuCl	Ag₂CO₃	V(Toluene)∶V(DMA)=1∶2	130	12	40
15	CuCl	Ag₂CO₃	V(Toluene)∶V(DMA)=1∶3	130	12	34
16^d	CuCl	Ag₂CO₃	Toluene	130	12	47
17	CuCl	Ag₂CO₃	V(Toluene)∶V(DMSO)=3∶1	130	12	67
18	CuCl	Ag₂CO₃	V(Toluene)∶V(DMF)=3∶1	130	12	50
19	CuCl	Ag₂CO₃	V(Toluene)∶V(DMF)=3∶1	110	12	32
20	CuCl	Ag₂CO₃	V(Toluene)∶V(DMF)=3∶1	150	12	39
21	CuCl	Ag₂CO₃	V(Toluene)∶V(DMF)=3∶1	130	8	58
22	CuCl	Ag₂CO₃	V(Toluene)∶V(DMF)=3∶1	130	16	66
23^e	CuCl	Ag₂CO₃	V(Toluene)∶V(DMF)=3∶1	130	12	25

酰胺噁唑啉导向的铜催化[2.2]对环芳烷直接C—H酰氧基化反应

Amide-Oxazoline-Directed Copper-Catalyzed C—H Acyloxylation of [2.2]Paracyclophanes

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