Me2AlSEt-Promoted Domino Dieckmann Cyclization Enables the Total Synthesis of Polycyclic Polyprenylated Acylphloroglucinols.

A bioinspired, Me2AlSEt-promoted domino Dieckmann cyclization via an 8-membered ring intermediate to construct bicyclo[3.3.1]nonanes was developed, and the divergent syntheses of nine complex polycyclic polyprenylated acylphloroglucinols were achieved. This novel domino cyclization tolerates a series of congested substrates, providing a very efficient way to construct diverse polycyclic structures. The selectivity and the advantages of the domino cyclization were studied. Moreover, the structure-activity relationship study leads to the identification of three simplified potent antitumor agents.