Scaffold Editing of Cubanes into Homocubanes, Homocuneanes via Cuneanes

The selective synthesis of cage‐type hydrocarbons through the editing of the highly symmetric molecule cubane can be anticipated as one of the efficient approaches. In this paper, we identify a catalyst that facilitates the efficient scaffold isomerization of cubanes into homocubanes. This approach, which involves the direct synthesis of homocubanol esters, is promising as a novel method for the synthesis of phenoxy bioisosteres. Additionally, we observed that the isomerization of 1,4‐bis(acyloxymethl)cubane results in the generation of both D2‐ and C2‐symmetrical bishomocubanes. The same catalyst was also applied to the isomerization of acyloxymethylcuneanes, producing homocuneanol esters. When benzoyl triflate was used as a catalyst on acyloxymethylcubane, a ring expansion of one carbon atom proceeded, resulting in the efficient production of acyloxymethylhomocubane. Additionally, we observed that the isomerization of 1,4‐diacyloxymethylcubane resulted in the generation of both D2‐ and C2‐symmetrical bishomocubanes. Similarly, 2‐acyloxymethylcuneane can also be converted into acyloxycuneane. This approach, which involves the direct synthesis of homocubanol and homocuneanol esters, is promising as a novel method for the synthesis of phenoxy bioisosteres.