Cu/Ni-Catalyzed Cyanomethylation of Alkenes with Acetonitrile for the Synthesis of β,γ-Unsaturated Nitriles

Saisai Zhang; Zengming Shen; Hong Jian

doi:10.1021/acs.joc.0c00141

Cu/Ni-Catalyzed Cyanomethylation of Alkenes with Acetonitrile for the Synthesis of β,γ-Unsaturated Nitriles

J Org Chem. 2020 May 1;85(9):6143-6150. doi: 10.1021/acs.joc.0c00141. Epub 2020 Apr 13.

Authors

Saisai Zhang¹, Zengming Shen¹, Hong Jian²

Affiliations

¹ Shanghai Key Laboratory for Molecular Engineering of Chiral Drugs, School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai 200240, China.
² Sixth People's Hospital South Campus, Shanghai Jiao Tong University, No. 6600 Nanfeng Road, Shanghai 201499, China.

PMID: 32227871
DOI: 10.1021/acs.joc.0c00141

Abstract

We have developed a protocol for the Cu/Ni-catalyzed cyanomethylation of alkenes with acetonitrile for the synthesis of β,γ-unsaturated nitriles. This is the first example of a direct coupling of the alkene sp² C-H bond and the acetonitrile sp³ C-H bond for the preparation of β,γ-unsaturated nitriles. Acetonitrile, an inexpensive and stable solvent, is demonstrated to be a useful cyanomethyl source. The combination of copper and nickel catalysts resulted in a high reaction efficiency.