Intermolecular Enamine Mizoroki–Heck Reactions on a Bio-Derived Scaffold

The intramolecular enamine-Mizoroki–Heck reaction allows for the construction of nitrogen-containing heterocycles, although the related intermolecular version is less known. The reactions of enamines derived from Cyrene were investigated under Mizoroki–Heck conditions. An optimization study was used to identify that 1.5 mol % Pd(dba)₂ with PCy₃ in xylene at reflux temperature gave the highest yield with electron-rich aryl iodides. Arylation occurred predominantly at the C–N center of the enamine, while the diastereoselectivity was dependent on the nitrogen substitution in the enamine.