Iron‐Catalyzed Cycloisomerization and C−C Bond Activation to Access Non‐canonical Tricyclic Cyclobutanes

Cycloisomerizations are powerful skeletal rearrangements that allow the construction of complex molecular architectures in an atom-economic way. We present here an unusual type of cyclopropyl enyne cycloisomerization that couples the process of a cycloisomerization with the activation of a C-C bond in cyclopropanes. A set of substituted non-canonical tricyclic cyclobutanes were synthesized under mild conditions using [(Ph3 P)2 Fe(CO)(NO)]BF4 as catalyst in good to excellent yields with high levels of stereocontrol.