Exploitation of high functional chiral building blocks by meso-asymmetrization using Ru^<II> catalyst.

在本研究项目中，作者应用Ru-手性胺配合物催化不对称氢转移反应得到手性KDP及其衍生物。首先，作者尝试了外消旋内烯丙醇的催化不对称氢转移反应。催化不对称氢转移反应在生成手性酮的同时生成了对映体富集醇。因此，反应损失了起始原料的一半，手性醇的产率最高可达50%。但在我的情况下，由于底物具有合适的结构背景，将得到手性烯酮和手性醇。事实上，手性烯丙醇和手性烯酮的最大得率分别为96%和54%ee。由于脂肪酶介导的动力学拆分方法不适用于α取代的外消旋内烯丙醇的动力学拆分，因此尝试了催化不对称氢转移反应来合成手性酮和手性烯丙醇。该反应实际上为手性烯酮和手性烯丙醇提供了良好的化学产率和较高的对映体过量，证明了不对称氢转移法是一种实用的拆分KDP衍生物的方法。作者利用得到的手性化合物合成了具有生物活性的天然产物(+)-古铜酚、(-)-戊霉素I和(+)-阿尼酮。

In this research project, the auther applied the catalytic asymmetric hydrogen transfer reaction using Ruthenium-chiral amine complex to obtain chiral KDP and its derivatives.First, the auther tried the catalytic asymmetric hydrogen transfer reaction of racemic endo-allyl alcohol.The catalytic asymmetric hydrogen transfer reaction proceeds to give enantiomerically enriched alcohols together with generation of achiral ketones.The reaction, therefore, loses one half of the starting material and the chiral alcohol will be obtained in maximum 50% yield. But in my case, as the substrate has an appropriate structural background, the chiral enone and the chiral alcohol will be obtained. In fact, the chiral allyl alcohol and the chiral enone were obtained in maximum 96% ee and 54% ee, respectively.As the lipase-mediated kinetic resolution was not useful method for kinetic resolution of the racemic α-substituted endo-allyl alcohols, the catalytic asymmetric hydrogen transfer reaction was tried to give chiral ketones and chiral allyl alcohols. The reaction, actually, provided the chiral enones and the chiral allyl alcohols in good chemical yields and also with high enantiomeric excess to prove the asymmetric hydrogen transfer method to be a practical method for the resolution of KDP derivatives .The auther utilized the obtained chiral compounds for the synthesis of the biological active natural products, (+)-curcuphenol, (-)-pentenomycin I and (+)- arnicenone.