Dipartimento Farmaco Chimico Tecnologico (DFCT), University of Siena, via Aldo Moro 2, 53100 Siena, Italy.
J Org Chem. 2010 Apr 2;75(7):2333-40. doi: 10.1021/jo1001559.
The first synthesis of the marine endoperoxide 9,10-dihydroplakortin, of its C10-desethyl analogue, and of their corresponding C6 epimers is described. Stereogenic centers at C4 and at the lateral chain have been stereoselectively synthesized through Evans' chiral auxiliary chemistry. Moreover, the reported synthesis features a one-pot three-step hydroperoxysilylation/cyclization reaction for the construction of the endoperoxide ring system. Homologation of the aldehyde resulting from diol cleavage through a Wittig-based strategy gave access to the ester-containing lateral chain at C3.
本文首次描述了海洋内过氧化物 9,10-二氢 Plakortin、其 C10-去乙基类似物及其相应的 C6 差向异构体的全合成。通过 Evans 手性辅基化学，立体选择性地合成了 C4 和侧链上的立体中心。此外，所报道的合成方法还具有通过一锅三步过氧硅氢化/环化反应构建内过氧化物环系统的特点。通过基于 Wittig 的策略对二醇断裂产生的醛进行同系化，可得到 C3 位含有酯基的侧链。
