无过渡金属催化的α-溴代茚酮自由基裂解反应合成(2-氰基苯基)乙酸-2,2,6,6-四甲基哌啶酯

doi:10.6023/cjoc202208006

有机化学 ›› 2023, Vol. 43 ›› Issue (6): 2171-2177.DOI: 10.6023/cjoc202208006 上一篇下一篇

研究论文

无过渡金属催化的α-溴代茚酮自由基裂解反应合成(2-氰基苯基)乙酸-2,2,6,6-四甲基哌啶酯

秦娇, 陈杰, 苏艳^*()

宁夏大学化学化工学院省部共建煤炭高效利用与绿色化工国家重点实验室银川 750021

收稿日期:2022-08-05 修回日期:2022-10-31 发布日期:2022-12-28
作者简介:
^† 共同第一作者
基金资助:
宁夏自然科学基金(2021AAC03100)

Synthesis of 2,2,6,6-Tetramethylpiperidin-1-yl-2-(2-cyanophenyl)-acetate by Transition Metal-Free Radical Cleavage Reaction from α-Bromoindanone

Jiao Qin, Jie Chen, Yan Su^*()

State Key Laboratory of High-Efficiency Coal Utilization and Green Chemical Engineering, College of Chemistry and Chemical Engineering, Ningxia University, Yinchuan 750021

Received:2022-08-05 Revised:2022-10-31 Published:2022-12-28
Contact: * E-mail: suyan@nxu.edu.cn
About author:
^† The authors contributed equally to this work
Supported by:
Ningxia Natural Science Foundation(2021AAC03100)

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摘要/Abstract

报道了溴代茚酮底物在叠氮化钠和2,2,6,6-四甲基哌啶氮氧化物共同作用下合成(2-氰基苯基)乙酸-2,2,6,6-四甲基哌啶酯的方法, 实现了溴代茚酮结构在无过渡金属催化条件下的自由基裂解反应, 合成了一系列芳基2-氰基-苯乙酸酯化合物, 拓展了氰基苯乙酸酯的合成方法, 并通过计算化学方法验证了这一反应的反应机理. 该反应条件温和、无需过渡金属催化剂、操作简便以及具有一定的底物普适性.

关键词: 茚酮, 2-氰基苯乙酸酯, 自由基裂解反应, 无过渡金属

In this paper, the synthesis of 2,2,6,6-tetramethylpiperidin-1-yl-2-(2-cyanophenyl)acetate from bromoindanone with sodium azide and 2,2,6,6-tetramethylpiperidine nitrogen oxide was reported. The carbon-carbon bond cleavage of bromoindenone was realized with transition metal-free catalysis and a series of aryl 2-cyano-phenylacetate compounds were obtained. This method was an expansion of cyanophenylacetate’ synthesis, and the reaction mechanism was verified by computational chemistry. The experiment was carried out under mild conditions with transition metal-free catalysis and with broad substrate scope.

Key words: indanone, 2-cyanophenylacetate, radical cleavage reaction, transition metal-free

引用此文

秦娇, 陈杰, 苏艳. 无过渡金属催化的α-溴代茚酮自由基裂解反应合成(2-氰基苯基)乙酸-2,2,6,6-四甲基哌啶酯[J]. 有机化学, 2023, 43(6): 2171-2177.

Jiao Qin, Jie Chen, Yan Su. Synthesis of 2,2,6,6-Tetramethylpiperidin-1-yl-2-(2-cyanophenyl)-acetate by Transition Metal-Free Radical Cleavage Reaction from α-Bromoindanone[J]. Chinese Journal of Organic Chemistry, 2023, 43(6): 2171-2177.

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图/表 6

图1. 含氰基天然产物和药物分子

Figure 1. Cyano-containing natural product and drug moleculars

图2. 叠氮参与的碳-碳键碎裂化反应

Figure 2. Carbon-carbon bond fragmentation with azide

Entry	TEMPO/equiv.	Solvent	Temp./℃	Yield/%
1^a	2.5	MeOH	0	75
2^a	2.5	MeCN	0	80
3^a	2.5	Acetone	0	55
4^a	2.5	DMSO	r.t.	Decompose
5^a	2.5	^tBuOH	0	51
6^a	2.5	DMF	0	>99
7^a	2.0	DMF	0	52
8^a	1.5	DMF	0	47
9^b	2.5	DMF	0	72
10^c	2.5	DMF	0	81

表1. 反应条件优化

Table 1. Optimization of the reaction conditions

表2. 氰基苯乙酸酯衍生物的制备

Table 2. Preparation of cyanophenylacetate derivatives

图3. 非2-茚酮反应底物拓展

Figure 3. Scope of other bromoindanone substrates

图4. 计算化学反应机理研究

Figure 4. Mechanism from computation

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无过渡金属催化的α-溴代茚酮自由基裂解反应合成(2-氰基苯基)乙酸-2,2,6,6-四甲基哌啶酯

Synthesis of 2,2,6,6-Tetramethylpiperidin-1-yl-2-(2-cyanophenyl)-acetate by Transition Metal-Free Radical Cleavage Reaction from α-Bromoindanone

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