Asymmetric Reaction of ferrocene Derivatives Using Microbe or Enzyme.

生物催化反应在有机合成中的应用已被证明是制备手性分子的一种非常实用和有效的方法。有机金属化合物在现代有机合成中的价值也得到了广泛的认识，有机金属化学与酶化学的结合提供了巨大的潜力。在同一环上具有两个不同取代基的二茂铁化合物是具有平面手性的光学活性化合物。本文研究了二茂铁化合物的微生物或酶转化反应，首先考察了哪些微生物可以对这些平面手性化合物进行对映选择性反应，其次发现了取代基位置和反应条件对该反应的影响。进行了三种反应：面包酵母还原反应、酯交换反应和脂肪酶水解反应。25个二茂铁1,2 -或1,3 -二取代的二茂铁化合物作为底物被合成。用发酵的面包酵母对映选择性还原，动力学分解了甲酰基二茂铁的外消旋2-或3-取代衍生物。此外，2-或3-取代的二茂铁羟甲基衍生物在有机溶剂（己烷或二异丙醚）中用乙烯酯进行酯交换，用脂肪酶进行光学分解。用面包酵母对二茂铁醛进行微生物不对称还原，得到了2-和3-不同取代基位置上的绝对构型相反的平面手性醇。二茂铁羟甲基衍生物与脂肪酶酯交换反应时，尽管反应时间较长，但产物的光学纯度与取代基大小有关。通过使用最合适的条件组合（酶、酰化试剂和溶剂），可以获得具有高光学纯度的手性二茂铁化合物。这些微生物反应的所有产物都可以用Prelog法则或象限法则来解释。少

The application of biocatalytic reaction to organic synthesis has been shown to be a Tiighly pratical and efficient means of preparing chiral molecules. The value of organometallic compoundd in modern organic synthesis has also been widely recognised, and a combination of organometallic and enzymatic chemistries of offers great potential. Ferrocene compounds which have two different substituents on the same ring are optically active compounds having planer chirality. We have invastigated microbial or enzymatic transformation reaction of these recemic ferrocene compounds, which have been done to survey what microorganisms can react enantioselectively to these planar chirality compounds, and secondly to f ind the some regularity in this reaction about influence of substituents position and reaction condition. Three kinds of reaction, baker's yeast reduction, transesterification or hydrolysis reaction with lipase have been performed. Twenty five ferrocene 1, 2- or 1, 3-disubstituted ferro … More cene compounds are synthesized as the substrates. Racemic 2- or 3-substituted derivatives of formylferrocene were kinetically resolved by enantioselective reduction with a fermenting baker's yeast. Moreover, 2- or 3-substituted derivatives of hydroxymethyl ferrocene were optically resolved with lipases by transesterification using vinyl esters in organic solvent(hexane or diisopropyl ether). In the microbial asymmetric reduction of ferrocene aldehyde with baker's yeast, planar chiral alcohol are obtained as opposite absolute configuration on different substituents position 2- and 3-. In the transesterification of hydroxymethyl ferrocene derivatives with lipase, optically purity of products depends of the substituent size despite of longer reaction time. Chiral ferrocene compounds having high optical purity are possible to obtained by using the most suitable combination of condition(enzyme, acylation reagent, and solvent). All the products of these microbial reaction are explained by Prelog's or Quadrant's rule. Less