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

doi:10.6023/cjoc202208006

Chinese Journal of Organic Chemistry ›› 2023, Vol. 43 ›› Issue (6): 2171-2177.DOI: 10.6023/cjoc202208006 Previous Articles Next Articles

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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Abstract

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

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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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Fig. & Tab. 6

Figure 1. Cyano-containing natural product and drug moleculars

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

Table 1. Optimization of the reaction conditions

Table 2. Preparation of cyanophenylacetate derivatives

Figure 3. Scope of other bromoindanone substrates

Figure 4. Mechanism from computation

References 24

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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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References 24

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