Methyl groups widely exist in bioactive molecules and site-specific methylation becomes a valuable strategy for their structural functionalization. Aiming to introduce this smallest alkyl handle, a high regioselective peri- and...

Natural methylated naphthalene compounds, possessing diverse biological activities, remain to be studied because of low content in plants and lacking synthetic methods. Herein, we have disclosed new approaches to methylated naphthalene natural products represented by dehydrocacalohastine and musizin from simple and commercially available naphthalene molecules with the assistance of our reported regioselective C−H methylation. The dehydrocacalohastine has been firstly synthesized from 1‐bromonaphthalen‐2‐ol in overall 8.9% yield with 8 steps. Additionally, the solution to musizin saved 2 steps with comparative yields to previous reported route.

A total synthetic approach of hemigossypol is described with 10 steps in 9.5 % total yield with the key feature being successive ligand-directed proximal C-H oxygenations. Direct functionalization of the...