上海交通大学学报

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2023 , Vol. 57 >Issue 10: 1245 - 1249

DOI: https://doi.org/10.16183/j.cnki.jsjtu.2022.108

化学化工

镍催化下乙腈为氰源的芳基三氟甲磺酸酯氰化反应

  • 周堃 ,
  • 沈增明
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  • 上海交通大学 化学化工学院,上海 200240
周堃(1997-),硕士生,从事金属有机化学研究.

收稿日期: 2022-04-11

  修回日期: 2022-12-19

  录用日期: 2022-12-30

  网络出版日期: 2023-03-18

基金资助

国家自然科学基金(21272001);国家自然科学基金(21672144);青海省科技部门(2020-ZJ-702);上海交通大学(YG2019QNB37)

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Nickel-Catalyzed Cyanation of Aryl Triflates Using Acetonitrile as a Cyano Source

  • Kun ZHOU ,
  • Zengming SHEN
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  • School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

Received date: 2022-04-11

  Revised date: 2022-12-19

  Accepted date: 2022-12-30

  Online published: 2023-03-18

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摘要

经典的氰化反应中多使用剧毒的金属氰源或合成复杂的有机氰源,这些氰源由于各自存在缺陷,都有一定局限性.将镍催化下低毒、廉价的乙腈作为氰源,以芳基三氟甲磺酸酯作为底物,对催化剂、配体、添加剂、温度等条件进行筛选,以物质的量分数为0.1的 Ni(OTf)2作为催化剂,物质的量分数为0.1的1, 3-双(二苯基膦)丙烷作为配体,物质的量分数为2的 Zn作为还原剂,物质的量分数为0.2的Zn(OTf)2作为添加剂,0.7 mL乙腈作为溶剂,氮气保护下,100 ℃反应60 h,成功实现芳基腈的高效合成.在该反应条件下,给电子取代基的底物展现出高效的反应性.该方法第一次实现镍催化下芳基三氟甲磺酸酯的氰化反应,成功使用绿色、经济的乙腈溶剂作为该反应的氰源.

关键词： 氰化反应; 乙腈; 镍催化; 亚胺中间体

本文引用格式

周堃 , 沈增明 . 镍催化下乙腈为氰源的芳基三氟甲磺酸酯氰化反应[J]. 上海交通大学学报, 2023 , 57(10) : 1245 -1249 . DOI: 10.16183/j.cnki.jsjtu.2022.108

Abstract

In classic cyanation reactions, toxic metal cyanide sources or complex organic cyanide sources are often used. Therefore, it is particularly important to develop a green and economical cyano source. Initially, 4-biphenylyl trifluoromethanesulfonate is chosen as the model substrate. Through extensive screening of catalysts, ligands, additives, reductant, temperature and other conditions, the optimal conditions are obtained (Ni(OTf)2, 1, 3-bis (diphenyphosphino)propane, Zn(OTf)2, Zn with a mole fraction of 0.1, 0.1, 0.2, 2, respectively, 0.7 mL CH3CN, N2, 60 h, 100 ℃). Subsequently, the generation and limitations of the substrates are studied under optimal conditions. It is found that substrates bearing electron-donating substituents exhibit an excellent efficiency for the cyanation of aryl trifluoromethanesulfonates. The cyanation of aryl trifluoromethanesulfonates is first realized under the catalysis of nickel with acetonitrile as a green and economical cyano source.

Key words： cyanation; acetonitrile; nickel catalyst; imine intermediate

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