Tortosa Mariola, Yakelis Neal A, Roush William R
Department of Chemistry, Scripps Florida, Jupiter, Florida 33458, USA.
J Org Chem. 2008 Dec 19;73(24):9657-67. doi: 10.1021/jo801794s.
A convergent and highly stereocontrolled total synthesis of the cytotoxic macrolide (+)-superstolide A is described. Key features of this synthesis include the use of bimetallic linchpin 36b for uniting the C(1)-C(15) (43) and the C(20)-C(27) (38) fragments of the natural product, a late-stage Suzuki macrocyclization of 49, and a highly diastereoselective transannular Diels-Alder reaction of macrocyclic octaene 4. In contrast, the intramolecular Diels-Alder reaction of pentaenal 5 provided the desired cycloadduct with lower stereoselectivity (6:1:1).
本文描述了细胞毒性大环内酯（+）-超斯托利德A的汇聚式且高度立体控制的全合成。该合成的关键特征包括使用双金属连接物36b连接天然产物的C(1)-C(15)（43）和C(20)-C(27)（38）片段、49的后期铃木大环化反应以及大环八烯4的高度非对映选择性跨环狄尔斯-阿尔德反应。相比之下，戊烯醛5的分子内狄尔斯-阿尔德反应提供了立体选择性较低的所需环加成物（6:1:1）。
