天然资源型化合物甾体皂苷元的化学研究

Chemistry of steroidal saponins as natural resource compounds

甾体皂苷元是一类重要的天然资源型化合物,它们已经被作为合成甾体药物的基本原料之一。为了能够实现高效、洁净并以"原子经济性"方式利用这类化合物资源,作者课题组系统地研究了甾体皂苷元的氧化降解反应。通过研究提供了用30%双氧水作为氧化试剂分别氧化伪甾体皂苷元和甾体甾苷元成为相应的孕烯酮醇、孕甾三醇、甾体-22-酸内酯以及系列含甲基侧链的双官能团手性合成试剂的实用方法和技术,进一步还研究了甾体皂苷元氧化降解产物在甾体药物、天然甾体活性分子和非甾体功能手性分子合成中的应用。作者课题组研究了甾体皂苷元螺环缩酮的溴代开环、胺代开环、内酯化溴代等反应,为利用甾体皂苷元完整骨架高效合成一些具有胆固醇基本结构的中药活性成分和具有重要生物活性的天然甾体化合物提供了新的思路和方法。

This article briefly summarizes our group′s systematic studies on the resource chemistry of steroidal sapogenins. Steroidal sapogenins are an important class of natural compounds,which could be utilized to synthesize various steroidal drugs. In order to achieve their efficient,clean and atom-economical utilization,our research group systematically investigated the oxidative degradation reaction of steroidal sapogenins.By employing 30% H 2O 2 as the oxidant, pseudo -sapogenins and sapogenins could be oxidized to the corresponding pregnenolone,pregnane-3 β,16,20-triol,steroidal 22-lactone,as well as a series of bifunctional reagents with chiral methyl group. These oxidative degradation products have been applied to the synthesis of steroidal drugs,biologically active natural steroidal molecules and non-steroid functional chiral molecules. Furthermore,we explored the bromination-ring opening,amination-ring opening and bromolactonization reactions of the spiroketal moiety,which provides new strategies and methods in the utilization of their intact skeleton to the efficient syntheses of active components of traditional Chinese medicines with the cholesterol skeleton,as well as biologically active steroidal natural products.