Total Syntheses of Borolithochromes A, D and G

Total syntheses of borolithochromes A, D and G, red pigments isolated from fossils of Jurassic putative red alga Solenopora jurassica, have been achieved. The benzo[gh]tetraphene skeletons of the borate ligands in these substances were constructed using Diels–Alder reactions of aryl dienes with naphthoquinone, followed by intramolecular Corey–Chaykovsky reactions. Complexation of these ligands with trimethyl borate generated homocomplexes, which upon sequential O-demethylation produced borolithochromes A and G. In the route to borolithochrome D, a heterocomplex was prepared by stepwise complexation of the ligands with 2-(dimethylamino)ethyl dimethyl borate. The strategy devised to accomplish the first total synthesis of borolithochromes A, D and G should be applicable to the preparation of other borolithochromes as well as spiroborates possessing two fused polycyclic aromatic ligands.