Controlling E/Z Selectivity in the Formation of Alkenyl Imines

Significance

The transition-metal-catalyzed syn addition of reagents across alkynes is an excellent process to synthesize substituted alkenes with high levels of stereocontrol. In the present communication, the authors report a rhodium-catalyzed silylation of alkynes, followed by addition to isonitriles. Remarkably, both E- and Z-stereoisomers can be obtained by modifying the isocyanide.