Total Synthesis Of Palodesangren B Trimethyl Ether And D Dimethyl Ether Via A Late-Stage Formation Of 2h-Pyran-2-One Of The Tetrahydrobenzo[C]Pyranochromenone Core

In four steps from the tricyclic core, palodesangren B trimethyl ether and palodesangren D dimethyl ether could be synthesized in 29 and 18% overall yields, respectively. A reaction sequence comprising the regioselective MgCl2-mediated Casnati-Skattebol ortho-formylation of phenol, Wittig methylenation, acryloylation, and Ru(II)-catalyzed ring-closing metathesis (RCM) led to the formation of the final 2H-pyran-2-one ring of the desired tetracyclic core.