K. Krohn et al., Total synthesis of angucyclines, part 14 - Biomimetic synthesis of the racemic angucyclinones of the aquayamycin and WP 3688-2 types, CHEM-EUR J, 6(21), 2000, pp. 3887-3896
The first synthesis of the racemic 8-deoxy WP3688-2 angucycline antibiotic
(3), with characteristic cis-hydroxy groups at C-4a and C-12b, is reported.
Key steps involve the coupling, mediated by samarium diiodide, of the bicy
clic trione 37 to the tricyclic cis-diol 39. Biomimetic aldol cyclization o
f the corresponding dione 41 gave a mixture of the tetracyclic cis- and tra
ns-3,4a-diols 42 and 43, which were oxidized by cerium ammonium nitrate to
the quinones 45 and 3. The synthetic compounds 45 and 3 corresponded in con
figuration to the angucycline antibiotics aquayamicin (1) and WP 3688-2 (2)
, respectively.