Pd/C-Catalyzed Stereoselective Arene Hydrogenation of Benzocyclobutenes Enabled by π-Bond Localization.

We developed here a Pd/C-catalyzed diastereoselective cis -hydrogenation of benzocyclobutene derivatives under mild conditions to deliver an array of bicyclo[4.2.0]octane scaffolds with up to five stereocenters. The π-bond localization enabled hydrogenation of the arene moiety to occur even at room temperature under 1 atm of a H 2 atmosphere.