Research of Quinuclidine-Promoted C—H Silylation of Electron- Deficient Nitrogen Heteroarenes

doi:10.6023/cjoc202110003

Chinese Journal of Organic Chemistry ›› 2022, Vol. 42 ›› Issue (4): 1136-1145.DOI: 10.6023/cjoc202110003 Previous Articles Next Articles

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奎宁环促进的缺电性含氮芳杂环碳氢硅基化反应研究

潘鹏^a, 袁启洋^a, 刘石惠^b, 赵建宏^a^,^*(), 张永强^a^,^*()

a 华东理工大学药学院上海 200237
b 嘉兴学院医学院浙江嘉兴 314001

收稿日期:2021-10-02 修回日期:2021-12-23 发布日期:2022-01-11
通讯作者: 赵建宏, 张永强
作者简介:
† 共同第一作者
基金资助:
国家自然科学基金(21871086)

Research of Quinuclidine-Promoted C—H Silylation of Electron- Deficient Nitrogen Heteroarenes

Peng Pan^a, Qiyang Yuan^a, Shihui Liu^b, Jianhong Zhao^a(), Yongqiang Zhang^a()

a School of Pharmacy, East China University of Science and Technology, Shanghai 200237
b College of Medicine, Jiaxing University, Jiaxing, Zhejiang 314001

Received:2021-10-02 Revised:2021-12-23 Published:2022-01-11
Contact: Jianhong Zhao, Yongqiang Zhang
About author:
† These authors contributed equally to this work.
Supported by:
National Natural Science Foundation of China(21871086)

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Abstract

Herein, a novel quinuclidine-promoted C—H silylation reaction using ammonium persulfate as the oxidant and hydrosilane as the silyl sourse was reported. The protocol proceeds via the hydrogen atom transfer-based formation of silyl radical and features mild and green reaction conditions, operational-simplicity, relatively easy scale-up, broad substrate scope and good functional group compatibility, providing a powerful tool for the facile introduction of silyl groups on electron- deficient nitrogen heteroarenes. Furthermore, in combination with the C—Si bond-based coupling reactions, the new reaction also offers a verstile platform for the rapid modification of electon-deficient nitrogen heteroarenes.

Key words: quinuclidine, electron-deficient nitrogen heteroarenes, hydrogen atom transfer, silyl radical, C—H silylation

Cite this article

Peng Pan, Qiyang Yuan, Shihui Liu, Jianhong Zhao, Yongqiang Zhang. Research of Quinuclidine-Promoted C—H Silylation of Electron- Deficient Nitrogen Heteroarenes[J]. Chinese Journal of Organic Chemistry, 2022, 42(4): 1136-1145.

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References 13

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Entry	Oxidant (x equiv.)	Additive (x equiv.)	Acid	Solvent	Yield^b/% of 3a
1	(NH₄)₂S₂O₈(3 equiv.)	A1 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	23
2	(NH₄)₂S₂O₈(3 equiv.)	—	—	V(DMSO)∶V(DCE)=1∶1	16
3	(NH₄)₂S₂O₈ (3 equiv.)	A2 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	18
4	(NH₄)₂S₂O₈ (3 equiv.)	A3 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	58^c
5	(NH₄)₂S₂O₈ (3 equiv.)	A4 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	44
6	(NH₄)₂S₂O₈ (3 equiv.)	A5 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	52
7	(NH₄)₂S₂O₈(3 equiv.)	A2 (3 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	50
8	(NH₄)₂S₂O₈ (3 equiv.)	A2 (1 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	49
9	Na₂S₂O₈ (3 equiv.)	A2 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	42
10	K₂S₂O₈(3 equiv.)	A2 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	43
11	(NH₄)₂S₂O₈(2 equiv.)	A3 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	21
12	(NH₄)₂S₂O₈(4 equiv.)	A3 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	47
13	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	DMSO	38
14	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	DCE	n.d^d
15	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	V(DMSO)∶V(DCM)=1∶1	22
16	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	V(DMSO)∶V(MeCN)=1∶1	37
17	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	V(MeCN)∶V(H₂O)=1∶1	n.d
18	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	V(DMSO)∶V(DCE)=4∶1	48
19	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶4	10
20	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	TsOH	[V(DMSO)∶V(DCE)=1∶1]	54
21	(NH₄)₂S₂O₈ (3 equiv.)	A3 (2 equiv.)	TFA	[V(DMSO)∶V(DCE)=1∶1]	5
22	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	Sc(OTf)₃	[V(DMSO)∶V(DCE)=1∶1]	49
23	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	[V(DMSO)∶V(DCE)=1∶1]	48^e
24	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	[V(DMSO)∶V(DCE)=1∶1]	52 ^f
25	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	[V(DMSO)∶V(DCE)=1∶1]	59^g
26	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	[V(DMSO)∶V(DCE)=1∶1]	46 ^h
27	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	[V(DMSO)∶V(DCE)=1∶1]	44 ⁱ
28	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	[V(DMSO)∶V(DCE)=1∶1]	Trace ^j

Entry	Oxidant (x equiv.)	Additive (x equiv.)	Acid	Solvent	Yield^b/% of 3a
1	(NH₄)₂S₂O₈(3 equiv.)	A1 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	23
2	(NH₄)₂S₂O₈(3 equiv.)	—	—	V(DMSO)∶V(DCE)=1∶1	16
3	(NH₄)₂S₂O₈ (3 equiv.)	A2 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	18
4	(NH₄)₂S₂O₈ (3 equiv.)	A3 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	58^c
5	(NH₄)₂S₂O₈ (3 equiv.)	A4 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	44
6	(NH₄)₂S₂O₈ (3 equiv.)	A5 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	52
7	(NH₄)₂S₂O₈(3 equiv.)	A2 (3 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	50
8	(NH₄)₂S₂O₈ (3 equiv.)	A2 (1 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	49
9	Na₂S₂O₈ (3 equiv.)	A2 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	42
10	K₂S₂O₈(3 equiv.)	A2 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	43
11	(NH₄)₂S₂O₈(2 equiv.)	A3 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	21
12	(NH₄)₂S₂O₈(4 equiv.)	A3 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶1	47
13	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	DMSO	38
14	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	DCE	n.d^d
15	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	V(DMSO)∶V(DCM)=1∶1	22
16	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	V(DMSO)∶V(MeCN)=1∶1	37
17	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	V(MeCN)∶V(H₂O)=1∶1	n.d
18	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	V(DMSO)∶V(DCE)=4∶1	48
19	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	V(DMSO)∶V(DCE)=1∶4	10
20	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	TsOH	[V(DMSO)∶V(DCE)=1∶1]	54
21	(NH₄)₂S₂O₈ (3 equiv.)	A3 (2 equiv.)	TFA	[V(DMSO)∶V(DCE)=1∶1]	5
22	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	Sc(OTf)₃	[V(DMSO)∶V(DCE)=1∶1]	49
23	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	[V(DMSO)∶V(DCE)=1∶1]	48^e
24	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	[V(DMSO)∶V(DCE)=1∶1]	52 ^f
25	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	[V(DMSO)∶V(DCE)=1∶1]	59^g
26	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	[V(DMSO)∶V(DCE)=1∶1]	46 ^h
27	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	[V(DMSO)∶V(DCE)=1∶1]	44 ⁱ
28	(NH₄)₂S₂O₈(3 equiv.)	A3 (2 equiv.)	—	[V(DMSO)∶V(DCE)=1∶1]	Trace ^j

奎宁环促进的缺电性含氮芳杂环碳氢硅基化反应研究

Research of Quinuclidine-Promoted C—H Silylation of Electron- Deficient Nitrogen Heteroarenes

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