Blue Light-Induced Formal Insertion Reaction of α-Siloxy Carbene into C—H Bond of 1,3-Diketones

doi:10.6023/cjoc202405026

Chinese Journal of Organic Chemistry ›› 2025, Vol. 45 ›› Issue (6): 2231-2238.DOI: 10.6023/cjoc202405026 Previous Articles Next Articles

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蓝光诱导的α-硅氧基卡宾与1,3-二酮C—H键的形式上插入反应

蒋馨雨^a, 张新科^a, 方曦^a, 徐新芳^b^,^*()

^a 中山大学药学院广州 510006
^b 浙江理工大学化学与化工学院杭州 310018

收稿日期:2024-05-17 修回日期:2024-06-30 发布日期:2024-07-25
通讯作者: 徐新芳
基金资助:
国家自然科学基金(22371309)

Blue Light-Induced Formal Insertion Reaction of α-Siloxy Carbene into C—H Bond of 1,3-Diketones

Xinyu Jiang^a, Xinke Zhang^a, Xi Fang^a, Xinfang Xu^b^,^*()

^a School of Pharmaceutical Sciences, Sun Yat-sen University, Guangzhou 510006
^b School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou 310018

Received:2024-05-17 Revised:2024-06-30 Published:2024-07-25
Contact: Xinfang Xu
Supported by:
National Natural Science Foundation of China(22371309)

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Abstract

A blue light-induced formal insertion reaction of α-siloxy carbene into the C—H bond of 1,3-diketones has been reported. Under the irradiation of blue light, acylsilane converts to α-siloxy carbene, which then undergoes formal C—H bond insertion reaction with the enol form of 1,3-diketone. This method uses readily available and relative stable acylsilane as carbene precursor, which features a simple and metal-free approach under mild conditions. Moreover, the synthetic potential of this protocol has been demonstrated by performing the reaction on a gram scale with comparable high yield.

Key words: photoinduction, α-siloxy carbene, 1,3-diketone, C—H bond insertion reaction

Cite this article

Xinyu Jiang, Xinke Zhang, Xi Fang, Xinfang Xu. Blue Light-Induced Formal Insertion Reaction of α-Siloxy Carbene into C—H Bond of 1,3-Diketones[J]. Chinese Journal of Organic Chemistry, 2025, 45(6): 2231-2238.

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Entry	Light source	1a∶2a	Solvent	Yield^b/%
1	10 W, 427 nm	1∶1	DCE	76
2	Dark	1∶1	DCE	0
3	10 W, 390 nm	1∶1	DCE	43
4	10 W, 450 nm	1∶1	DCE	52
5	10 W, 470 nm	1∶1	DCE	47
6	10 W, 427 nm	1.5∶1	DCE	86
7	10 W, 427 nm	2∶1	DCE	86
8	10 W, 427 nm	1.5∶1	DCM	83
9	10 W, 427 nm	1.5∶1	CHCl₃	78
10	10 W, 427 nm	1.5∶1	Hexane	53
11	10 W, 427 nm	1.5∶1	Xylene	61
12	10 W, 427 nm	1.5∶1	Toluene	50
13	10 W, 427 nm	1.5∶1	PhCl	94
14	10 W, 427 nm	1.5∶1	THF	23
15	10 W, 427 nm	1.5∶1	DMF	15
16^c	10 W, 427 nm	1.5∶1	PhCl	93
17^c^,^d	10 W, 427 nm	1.5∶1	PhCl	92
18^c^,^e	10 W, 427 nm	1.5∶1	PhCl	81

Entry	Light source	1a∶2a	Solvent	Yield^b/%
1	10 W, 427 nm	1∶1	DCE	76
2	Dark	1∶1	DCE	0
3	10 W, 390 nm	1∶1	DCE	43
4	10 W, 450 nm	1∶1	DCE	52
5	10 W, 470 nm	1∶1	DCE	47
6	10 W, 427 nm	1.5∶1	DCE	86
7	10 W, 427 nm	2∶1	DCE	86
8	10 W, 427 nm	1.5∶1	DCM	83
9	10 W, 427 nm	1.5∶1	CHCl₃	78
10	10 W, 427 nm	1.5∶1	Hexane	53
11	10 W, 427 nm	1.5∶1	Xylene	61
12	10 W, 427 nm	1.5∶1	Toluene	50
13	10 W, 427 nm	1.5∶1	PhCl	94
14	10 W, 427 nm	1.5∶1	THF	23
15	10 W, 427 nm	1.5∶1	DMF	15
16^c	10 W, 427 nm	1.5∶1	PhCl	93
17^c^,^d	10 W, 427 nm	1.5∶1	PhCl	92
18^c^,^e	10 W, 427 nm	1.5∶1	PhCl	81

蓝光诱导的α-硅氧基卡宾与1,3-二酮C—H键的形式上插入反应

Blue Light-Induced Formal Insertion Reaction of α-Siloxy Carbene into C—H Bond of 1,3-Diketones

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Fig. & Tab. 5

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