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 PCy 3 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.