The potent antitumor agent phorboxazole A was synthesized from six subunits comprising C1–C2 (115), C3–C8 (98), C9–C19 (74), C20–C32 (52), C33–C41 (84) and C42–C46 (85). Tetrahydropyrans B and C containing cis-2, 6-disubstitution were fabricated via palladium (II)-mediated intramolecular alkoxycarbonylation which, in the case of tetrahydropyran C, was carried out with catalytic palladium (II) and p-benzoquinone as the stoichiometric re- ...