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

doi:10.6023/cjoc202602012

摘要/Abstract

报道了一种基于廉价金属铜催化、利用酰胺噁唑啉导向基团实现的[2.2]对环芳烷直接C(sp²)—H酰氧化反应. 该反应体系适用于芳香羧酸、烯基羧酸及烷基羧酸等多种羧酸底物, 能以中等到良好的产率获得目标产物. 克级规模实验及后续水解反应进一步证明了该方法的合成实用性. 本研究为[2.2]对环芳烷的选择性官能化提供了一种高效、便捷的合成策略, 具有潜在的应用前景.

关键词: 铜催化, 酰胺噁唑啉导向, C—H酰氧基化, [2.2]对环芳烷

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

引用此文

韩银松, 王东炜, 肖佳怡, 冯若昆. 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[J]. 有机化学, 2026, 46(8): 3147-3157.

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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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