The synthesis of two diastereomeric members of the lycorane alkaloid family is reported. Although the routes are quite different in their approach, both involve the use of photochemistry as a key step, enabling the synthesis of gram quantities in the case of β-lycorane.

At hree-step synthesis of the 2-azabicyclo[3.3.1]nonaner ing system from simple pyrroles, employing a combined photochemical/palladium-catalysed approach is reported. Substrate scope is broad,a llowing the incorporation of aw ider ange of functionalityr elevant to medicinal chemistry.M echanistic studies demonstrate that the processo ccurs by acid-assisted CÀNb ond cleavage followed by b-hydride eliminationt of orm ar eactive diene, demonstratingt hat efficient control of what mightb e considered off-cycle reactionsc an result in productive tandem catalytic processes. This represents as hort and versatile route to the biologically important morphan scaffold.