Asymmetric Total Syntheses of (−)‐α‐Lycorane, (−)‐Zephyranthine,and Formal Synthesis of (+)‐Clivonine

An asymmetric route to (?)‐α‐lycorane and (?)‐zephyranthine, and a formal total synthesis of (+)‐clivonine were achieved. A pivotal intermediate, which serves as a potent precursor for the divergent syntheses of these natural products, was accessed by a diastereoselective Pd‐catalyzed cinnamylation of an N ‐tert ‐butanesulfinyl imine.