Synthesis of Chiral, Fused Tricyclic Molecules by Sequential Metal‐Catalyzed Reactions of Simple Substrates

A set of complex tricyclic compounds containing several functional groups and multiple stereogenic centers has been prepared in only two steps with excellent diastereo- and enantioselectivities. The synthesis takes advantage of the highly versatile and enantioselective Pd-catalyzed allylic substitution of simple cyclic allylic acetates or carbonates to form chiral 1,6-, 1,7- and 1,8-enynes, which are then diastereoselectively transformed to the corresponding cyclopentenone- and cyclobutene-based tricyclic compounds.