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

doi:10.6023/A16090480

Acta Chim. Sinica ›› 2017, Vol. 75 ›› Issue (1): 115-118.DOI: 10.6023/A16090480 Previous Articles Next Articles

Special Issue: 有机光化学

Article

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).

1. Halogen-Bond-Promoted Radical Isocyanide Insertion of o-Diisocyanoarenes with Perfluoroalkyl Bromides under Visible Light Irradiation.PDF(3868KB)

Abstract

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

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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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