160531-32-8Relevant articles and documents
Directed hydrogenations and an Ireland-Claisen rearrangement linked to Evans-Tishchenko chemistry: The highly efficient total synthesis of the marine cyclodepsipeptide doliculide
Chen, Tao,Altmann, Karl-Heinz
supporting information, p. 8403 - 8407 (2015/06/02)
Two new convergent total syntheses have been developed for the cytotoxic, actin microfilament-stabilizing marine cyclodepsipeptide doliculide (1). A key strategic element of both routes is the establishment of the central stereogenic center of the characteristic polydeoxypropionate stereotriad by means of a hydroxyl-directed catalytic hydrogenation of a trisubstituted double bond. The requisite olefin substrates were obtained through a modified Suzuki-Miyaura coupling or through Ireland-Claisen rearrangement of a propionate ester, respectively; the latter was the direct result of a highly selective Evans-Tishchenko reduction of a hydroxy ketone that had been obtained in a stereoselective Paterson aldol reaction. Doliculide (1) was finally obtained in a total number of 17 or 15 (14) linear steps, respectively, which represents a substantial improvement over previous syntheses of this highly bioactive natural product.
Enantioselective Total Synthesis of Doliculide, a Potent Cytotoxic Cyclodepsipeptide of Marine Origin and Structure-Cytotoxicity Relationships of Synthetic Doliculide Congeners
Ishiwata, Hiroyuki,Sone, Hiroki,Kigoshi, Hideo,Yamada, Kiyoyuki
, p. 12853 - 12882 (2007/10/02)
The total synthesis of doliculide (1), a potent cytotoxic cyclodepsipeptide from the Japanese sea hare Dolabella auricularia, has been achieved.The key step of the synthesis is the construction of the sereogenic centers of a 15-carbon polyketide-derived d
