Modular Syntheses of Phenanthro­indolizidine Natural Products

A highly concise strategy for the total synthesis of phenanthro­indolizidines was developed. The one-pot iterative Suzuki–Miyaura reaction of aryl boronic acids with <i>ortho</i>-bromoaryl <i>N</i>-methyliminodiacetate (MIDA) boronate followed by a second Suzuki–Miyaura reaction with a suitable pyridyl bromide provided <i>ortho</i>-aza-terphenyls. Subsequent saturation of the triple bond, treatment with mesyl chloride, and reduction of the resulting dihydroindolizidinium ring afforded the hexahydroindolizines. A final vanadium-catalyzed oxidative electrocyclization provided the desired alkaloids in only three column-separation operations.