Apoptolidin derivatives

Pennington JD, Williams HJ, Salomon AR, Sulikowski GA (2002) Toward a stable apoptolidin derivative identification of isoapoptolidin and selective deglycosylation of apoptolidin. Org Lett 4 3823-3825... 

In a related study, which also utilized peptide ent-46, we were able to access three hitherto untested acetyl derivatives, 47-49, of the highly potent and tumor-selective cytotoxic natural product apoptolidin A (41) [97]. Triacetates 48 and 49 were particularly significant, as a known problematic stractural rearrangement of... 

Fig. 5 (a) Apoptolidin A (41) derivatives accessed by site-selective acylation reactions using peptide em-46 [97], (b) Rearrangement of 41 to isoapoptolidin (50) [98,99]... 

Vinyl-vinyl coupling was extensively used for the preparation of polyconjugated systems and widely applied to the preparation of complex natural molecules such as Cochlemycin A, [77] (-t)-Crocacin D [78] (Scheme 6.10), Gambierol [79], Bafilo-mycin Vi [80], (-)-Sanglifehrin A [81] and Apoptolidin [82]. Stille coupling of a vinylstarmane with cyclic vinyl halides was used for the preparation of Himbadne derivatives [83]. 

---