A convergent synthetic method for the synthesis of fluorene derivatives has been developed by devising a rhodium‐catalyzed stitching reaction/alkene isomerization sequence. The reactions proceed smoothly under mild conditions for a variety of substrate combinations, and extended π‐conjugation systems are also readily accessible by utilizing this synthetic method. Optical properties of the obtained fluorene derivatives have also been examined.

A three-component synthesis of multisubstituted fluorene derivatives has been developed by devising a rhodiumcatalyzed stitching reaction/remote nucleophilic substitution sequence. A variety of nucleophiles can be installed in the second step including both heteroatom and carbon nucleophiles. An efficient synthesis of 5H-benzo[a]fluoren-5-ones has also been realized using N-(2-alkynyl)benzoylpyrrole as the reaction partner through a new reaction pathway.