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

doi:10.16183/j.cnki.jsjtu.2022.108

Abstract

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

CLC Number:

O621.3

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.

Figures/Tables 4

References 28

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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