Catalytic Direct Cyanomethylenation of C(sp3)-H Bonds via a One-Step Double C-C Bond Formation

An elegant and catalytic procedure for the one-step cyanomethylenation of C(sp(3))-H bonds adjacent to benzazoles and ketones is described herein using DMF as a C-1 unit and TMSCN as the cyanide source. The copper-mediated reaction between DMF and TMSCN gives a cyanomethylene radical intermediate that reacts with 2-alkylbenzazoles or alkylketones to furnish desired cyanomethylenated compounds under palladium catalysis. Subsequent interconversion of cyanomethylenated products makes the protocol synthetically attractive.

Automated summary

An elegant and catalytic procedure for the one-step cyanomethylenation of C(sp(3))-H bonds adjacent to benzazoles and ketones is described. The method involves using DMF as a C-1 unit and TMSCN as the cyanide source, and the copper-mediated reaction between DMF and TMSCN produces a cyanomethylene radical intermediate. This intermediate reacts with 2-alkylbenzazoles or alkylketones under palladium catalysis to yield the desired cyanomethylenated compounds. The subsequent interconversion of the cyanomethylenated products enhances the synthetic attractiveness of the protocol.