Department of Chemistry, University of Saskatchewan , 110 Science Place, Saskatoon, SK S7N 5C9, Canada.
Org Lett. 2016 Aug 5;18(15):3794-7. doi: 10.1021/acs.orglett.6b01798. Epub 2016 Jul 13.
The putative contiguous polypropionate precursor of dolabriferol was synthesized using as the key step a rationally designed enantiomer-selective aldol coupling (i.e., with kinetic resolution) of a racemic C1-C8 ketone fragment with an enantiopure C9-C15 aldehyde fragment. When exposed to alumina, the precursor was cleanly transformed into dolabriferol via a regioselective retro-Claisen fragmentation, providing the first experimental evidence for the proposed origin of dolabriferol and demonstrating that it is a plausible isolation artifact.
利用合理设计的对映选择性羟醛缩合（即动力学拆分），将外消旋的 C1-C8 酮片段与手性 C9-C15 醛片段偶联，合成了假定的连续聚丙交酯前体 dolabriferol。当暴露在氧化铝上时，该前体通过区域选择性的 retro-Claisen 断裂，干净地转化为 dolabriferol，为 dolabriferol 的提出的起源提供了第一个实验证据，并证明它是一个合理的分离假象。
