Total Synthesis of the Naturally Occurring <i>Amaryllidaceae</i> Alkaloid (+)‐Zephycitrine

The first catalytic asymmetric total synthesis of the naturally occurring Amaryllidaceae alkaloid, (+)‐zephycitrine ( 1a ), has been accomplished. This efficient 11‐step route (8.3% overall yield) establishes the key stereocenters using an organocatalytic Corey–Itsuno reduction. The construction of the complex core structure, featuring three contiguous stereocenters, was subsequently realized via a Mitsunobu reaction and a microwave‐assisted intramolecular carbonyl‐ene reaction. The synthesis was completed with a final Pictet–Spengler cyclization. This concise approach, employing a sequence of classical and robust reactions, provides a versatile and efficient platform for accessing pro‐drug derivatives and other members of the Amaryllidaceae alkaloid family.