Modular Total Syntheses of Lamellarin G Trimethyl Ether and Lamellarin S

Modular total syntheses of the title compounds 2 and 3 are reported. The key pyrrolic building block 8 was prepared from the readily accessible pyrrole 6 via a di‐iodination/mono‐deiodination sequence. Suzuki–Miyaura cross‐coupling of compound 8 with boronate ester 9 afforded lactone 10 . Bromination of compound 10 followed by N ‐alkylation under Mitsunobu conditions afforded the fully substituted pyrrole 13 that engaged in a second Suzuki–Miyaura cross‐coupling reaction with boronic acid 14 to give compound 15 . Hydrolysis of the ester moiety within the last compound afforded acid 16 that engaged in a decarboxylative Heck cyclization process to give lamellarin G trimethyl ether ( 3 ). A related sequence of reactions starting from building block 8 and using the isopropoxy‐substituted arenes 22 , 25 and 27 has allowed for the completion of the first total synthesis of lamellarin S ( 2 ).