镍催化下乙腈为氰源的芳基三氟甲磺酸酯氰化反应

doi:10.16183/j.cnki.jsjtu.2022.108

上海交通大学学报 ›› 2023, Vol. 57 ›› Issue (10): 1245-1249.doi: 10.16183/j.cnki.jsjtu.2022.108

所属专题：《上海交通大学学报》2023年“化学化工”专题

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()

上海交通大学化学化工学院,上海 200240

收稿日期:2022-04-11 修回日期:2022-12-19 接受日期:2022-12-30 出版日期:2023-10-28 发布日期:2023-11-01
通讯作者: 沈增明 E-mail:shenzengming@sjtu.edu.cn
作者简介:周堃(1997-),硕士生,从事金属有机化学研究.
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)

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

ZHOU Kun, SHEN Zengming()

School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

Received:2022-04-11 Revised:2022-12-19 Accepted:2022-12-30 Online:2023-10-28 Published:2023-11-01
Contact: SHEN Zengming E-mail:shenzengming@sjtu.edu.cn

摘要/Abstract

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

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

中图分类号:

O621.3

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.

ZHOU Kun, SHEN Zengming. Nickel-Catalyzed Cyanation of Aryl Triflates Using Acetonitrile as a Cyano Source[J]. Journal of Shanghai Jiao Tong University, 2023, 57(10): 1245-1249.

图/表 4

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镍催化下乙腈为氰源的芳基三氟甲磺酸酯氰化反应

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

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条目	催化剂	配体	添加剂	产率^① /%
1	Ni(OTf)₂	dppb	-	20
2	Ni(OTf)₂	dppe	-	11
3	Ni(OTf)₂	dppf	-	22
4	Ni(OTf)₂	dppp	-	71(70^②)
5	Ni(acac)₂	dppp	-	53
6	NiCl₂	dppp	-	62
7	Ni(OTf)₂	dppp	ZnCl₂	70
8	Ni(OTf)₂	dppp	ZnF₂	66
9	Ni(OTf)₂	dppp	Mg(OTf)₂	65
10	Ni(OTf)₂	dppp	Tf₂O	83
11	Ni(OTf)₂	dppp	Zn(OTf)₂	88
12^③	Ni(OTf)₂	dppp	Zn(OTf)₂	87
13^④	Ni(OTf)₂	dppp	Zn(OTf)₂	0
14^{③, ⑤}	Ni(OTf)₂	dppp	Zn(OTf)₂	89^②
15^{③, ⑥}	Ni(OTf)₂	dppp	Zn(OTf)₂	70

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