可见光照射下卤键引发的多氟烷基溴化物与邻二芳基异腈的自由基型插入反应

doi:10.6023/A16090480

化学学报 ›› 2017, Vol. 75 ›› Issue (1): 115-118.DOI: 10.6023/A16090480 上一篇下一篇

所属专题：有机光化学

研究论文

可见光照射下卤键引发的多氟烷基溴化物与邻二芳基异腈的自由基型插入反应

孙晓阳^a, 王文敏^b, 马晶^b, 俞寿云^a

a 南京大学化学化工学院生命分析化学国家重点实验室南京 210023;
b 南京大学化学化工学院理论与计算化学研究所南京 210023

投稿日期:2016-09-07 修回日期:2016-09-26 发布日期:2016-09-27
通讯作者: 俞寿云,E-mail:yushouyun@nju.edu.cn,Tel.:86+25-89684717;马晶,E-mail:majing@nju.edu.cn,Tel.:86+25-89684717 E-mail:yushouyun@nju.edu.cn;majing@nju.edu.cn
基金资助:
项目受国家自然科学基金面上项目资助（Nos.21672098，21472084，21273102）.

Halogen-Bond-Promoted Radical Isocyanide Insertion of o-Diisocyanoarenes with Perfluoroalkyl Bromides under Visible Light Irradiation

Sun Xiaoyang^a, Wang Wenmin^b, Ma Jing^b, Yu Shouyun^a

a State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023;
b Institute of Theoretical and Computational Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023

Received:2016-09-07 Revised:2016-09-26 Published:2016-09-27
Supported by:
Project supported by the National Natural Science Foundation of China (Nos. 21672098, 21472084, 21273102).

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1. 可见光照射下卤键引发的多氟烷基溴化物与邻二芳基异腈的自由基型插入反应.PDF(3868KB)

摘要/Abstract

报道了一种由卤键引发的自由基型双异腈插入反应.多氟烷基溴化物作为卤键的给体，有机碱作为卤键的受体.在可见光照射下，卤键复合物发生单电子转移过程生成多氟烷基自由基，被邻二芳基异腈捕获生成2-多氟烷基化喹喔啉衍生物.该反应在室温条件下进行，产率高，底物适用性广.反应的自由基属性可以通过EPR实验验证.2-多氟烷基化喹喔啉衍生物中3-位氢源可以通过氘代实验确定，实验显示氢源来自于有机碱和溶剂，而且溶剂是最主要的氢源.

关键词: 卤键, 可见光, 异腈, 氟烷基化, 喹喔啉, 自由基

A halogen-bond-promoted double radical isocyanide insertion of o-diisocyanoarenes with perfluoroalkyl bromides is reported, in which perfluoroalkyl bromides as halogen bond donors and organic bases as halogen bond acceptors. Fluoroalkyl radicals can be generated by a visible-light-induced single electron transfer (SET) process. Fluoroalkyl radicals are trapped by o-diisocyanoarenes to give 2-fluoroalkylated quinoxaline derivatives. These reactions could be carried out under mild conditions with good chemical yields and broad substrate scope. A broad range of fluoroalkyl bromides with different functionalities could undergo this reaction to give the corresponding quinoxaline derivatives in good yields. A variety of o-diisocyanides could be fluoroalkylated to give quinoxalines under our established conditions. The radical nature of this reaction was confirmed by electron paramagnetic resonance (EPR) experiments using tert-butyl-α-phenylnitrone (PBN) as a spin trap. When PBN was introduced into the reaction mixture, a spectrum signal attributed to the spin adduct C₈F₁₇-PBN appeared as a triplet of doublets. Without light and amine, almost no signal was observed. These phenomena strongly suggested that the perfluoroalkyl radical was the key intermediate and the generation of the intermediate heavily relied on the presence of light and amine. A series of deuteration experiments were performed and these results suggested that both the amine and solvent could serve as the hydrogen source and solvent was the major source.

Key words: halogen bond, visible light, isocyanide, fluoroalkylation, quinoxaline, radical

引用此文

孙晓阳, 王文敏, 马晶, 俞寿云. 可见光照射下卤键引发的多氟烷基溴化物与邻二芳基异腈的自由基型插入反应[J]. 化学学报, 2017, 75(1): 115-118.

Sun Xiaoyang, Wang Wenmin, Ma Jing, Yu Shouyun. Halogen-Bond-Promoted Radical Isocyanide Insertion of o-Diisocyanoarenes with Perfluoroalkyl Bromides under Visible Light Irradiation[J]. Acta Chim. Sinica, 2017, 75(1): 115-118.

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可见光照射下卤键引发的多氟烷基溴化物与邻二芳基异腈的自由基型插入反应

Halogen-Bond-Promoted Radical Isocyanide Insertion of o-Diisocyanoarenes with Perfluoroalkyl Bromides under Visible Light Irradiation

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