Development of practical synthetic method for preparation of alcohols in chiral from.

如果生物活性化合物具有不对称中心，则两个对映体通常表现出不同的生物活性。因此，需要开发一种对映体，而不是外消旋化合物，作为药物或农用化学品。因此，寻找可行的工业规模生产方法一直是有机合成的重要课题。本研究的目的是开发一种高效、实用的光纯醇合成方法。由于醇包埋在各种生物活性物质中，并且已被广泛接受为合成天然化合物的有用中间体，因此人们强烈期待制备光学活性醇的实用合成方法。烯丙基硅烷的Sharpless不对称二羟基化反应和随后的Petterson反应产生了高收率的光学活性烯丙醇。炔的夏普利斯不对称二羟基化反应得到在-位置有另一个羟基的丙炔醇。将这些二醇加氢氧化化，然后用醛或CO_2处理，分别得到手性形式的糠醇或丁烯内酯。利用这些手性醇作为手性构件，合成了一些生物化合物。

If biologically active compounds have asymmetric center, the two enantiomers, usually, show differnent biological activities. Thus it has been required to develop one enantiomer, not racemic compound, as drugs or agricalutural chemicals. The development of practical method which can be viable in indurially scale production, therefore, has been the important subject in organic synthesis. The purpose of the present research is the development of efficient and practical method for synthesis of alcohols in optically pure from. Since alcohols are embeded in various kinds of biologically active substances and also have been widely accepted as useful intermediates for synthesis of natural compounds, the practical synthetic methodolgy for preparation of optically active alcohols has been strongly anticipated.The Sharpless asymmetric dihydroxylation of allyl silane followed by the Petterson reaction provided optically active allyl alcohols in excellent yields. The Sharpless asymmetric dihydroxylation of enyne gave propargylic alcohols having another hydroxyl group at beta-position. Hydromagnesiation of these diols followed by treatment with aldehyde or CO_2 provided furyl alcohols or butenolides, respectively, in a chiral form. By using these chiral alcohols as chiral building block, a few biological compounds were synthesized.