Stereoselective Synthesis of Acyclic Tetrasubstituted Alkenes from Anilines by Dearomatization and Trimethylenemethane Cycloaddition.

A method for stereoselective construction of acyclic all-carbon tetrasubstituted alkenes through insertion of nitrile-substituted trimethylenemethane into the aryl C-N bond in anilines via an aromaticity destruction-reconstruction process is reported. The process involves dearomatization, azo-[3 + 2] TMM cycloaddition and aromatization-triggered rearrangement.