This perspective article provides a general overview of the most relevant topics in the applications of chiral metallic organophosphates. A brief introduction along with a historic comparative profile of the BINOL and phosphoric acid analogues are given. Next, a selection of the most outstanding uses of the catalysts according to the employed metal is presented.

Novel chiral catalytic systems based on both organic compounds and metal salts have been developed for the enantioselective [3 + 2] cycloaddition of münchnones onto fullerenes and olefins. These two different approaches proved to be efficient and complementary in the synthesis of optically active pyrrolino[3,4:1,2][60]fullerenes with high levels of enantiomeric excess and moderate to good conversions. Further functionalization of the pyrrolinofullerene carboxylic acid derivatives has been carried out by esterification and amidation reactions.