A Chemoenzymatic Total Synthesis of (+)-Clividine

The title compound, <i>ent</i>-<b>1</b>, the non-natural enantiomeric form of the lycorenine-type alkaloid (−)-clividine (<b>1</b>), has been prepared using the enantiomerically pure (ee >99.8%) <i>cis</i>-1,2-dihydrocatechol <b>3</b> as starting material. A key feature associated with the closing stages of the synthesis involved the diastereoselective addition of a nitrogen-centered radical onto a pendant cyclohexene to establish the cis-fused D-ring and the required stereochemistry at C11b in the final product <i>ent</i>-<b>1</b>.