Catalytic Asymmetric Total Synthesis of Naturally Occurring <i>Amaryllidaceae</i> Alkaloid, (+)-11-Hydroxyvittatine

The first catalytic asymmetric total synthesis of naturally occurring (+)-11-hydroxyvittatine (<b>1a</b>) has been achieved in 9 steps and an overall yield of 14.4%. The enantioselectivity was achieved using an organocatalytic Corey-Itsuno reduction. Subsequent Mitsunobu reaction and a microwave-assisted intramolecular carbonyl-ene reaction enabled the construction of the core structure with three fixed stereocenters. Finally, a Pictet-Spengler cyclization completes the total synthesis of (+)-11-hydroxyvittatine (<b>1a</b>). Our synthesis relies on simple and classical reactions to address the <i>Amaryllidaceae</i> alkaloids and will serve as an efficient route to access the other congeners.