A new method has been developed for the synthesis of tetrahydro-2H-fluorenes based on a Pd(0)-catalyzed benzylic C(sp(3) )-H functionalization. Importantly, the success of the cyclization step was dependent on there being substituents at the two positions ortho to the benzylic group to avoid an undesired C(sp(2) )-H functionalization. This method was subsequently used to prepare the right-hand fragment of the hexacyclic triterpenoid benzohopanes, and therefore represents a powerful tool for the construction of the related compounds.

It is important for the construction of the desired scaffold, building block of various types of natural products, that the o‐tolyl part of the substrates bears a second o‐substituent.