Amans Dominique, Bellosta Véronique, Cossy Janine
Laboratoire de Chimie Organique associé au CNRS, ESPCI, 10 rue Vauquelin, 75231 Paris Cedex 05, France.
Org Lett. 2007 Apr 12;9(8):1453-6. doi: 10.1021/ol070240k. Epub 2007 Mar 14.
[structure: see text] The monomeric counterpart of marinomycin A, an antitumor-antibiotic marine natural product, was synthesized efficiently in 11 steps from the commercially available ethyl (R)-(-)-3-hydroxybutyrate. The strategy was highlighted by a crucial regio- and stereoselective cross-metathesis to form the C20-C21 double bond, enantioselective allyltitanations to control the configuration of the C17, C23, and C25 stereogenic centers, and a stereocontrolled construction of the tetraene moiety based on an original Horner-Wadsworth-Emmons olefination followed by a Pd-catalyzed cross-coupling.
[结构：见正文] 抗肿瘤抗生素海洋天然产物马利诺霉素A的单体类似物，以市售的(R)-(-)-3-羟基丁酸乙酯为原料，经11步反应高效合成。该策略的突出之处在于关键的区域和立体选择性交叉复分解反应以形成C20-C21双键、对映选择性烯丙基钛化反应以控制C17、C23和C25手性中心的构型，以及基于原始的霍纳尔-沃兹沃思-埃蒙斯烯化反应随后进行钯催化交叉偶联反应的四烯部分的立体控制构建。
