Enantioresolution of Alcohols and its Application to Organic Synthesis

(S)-(（+）-2-甲氧基-2-（1-萘基）丙酸又称（S）-（+）-MαNP酸，是由Nobuyuki Harada教授、Shunsike Yohara博士和我共同设计的，它有两个作用：一是分离仲醇的非对映异构体，二是同时测定醇的羟基的绝对构型。我们注意到了这种新型手性助剂的这些作用，并报道了利用这种手性助剂合成各种光学活性的芳基甲醇和二芳基甲醇。我们还重点介绍了4-丁基苯酞被称为芹菜油的主要香料确定其研究开始于19世纪90年代。利用不对称合成机理推测了4-丁基苯酞的绝对构型。最终确定该香料的结构为（S）-（-）-4-丁基苯酞。我们还成功地合成了两个对映异构体的松茸香料称为“松竹醇”。众所周知，对含脂肪族长链的醇进行对映体拆分和确定羟基的绝对构型是困难的。也没有关于此类醇的不对称合成的报道。最近，我们成功地拆分了由油酸制备的36碳醇，并测定了其羟基的绝对构型。这为合成具有生物活性的长链脂肪族取代醇类化合物提供了一条新的途径。

(S)-(+)-2-Methoxy-2-(1-naphthyl)propionic acid so-called (S)-(+)-MαNP Acid, which was devised together by Professor Nobuyuki Harada, Dr shunsike Kuwahara and myself, has two roles ; one is diastereomeric separation of secondary alcohols and the other is simultaneous determination of absolute configuration of the hydroxyl group of the alcohols. We have paid our attention to these roles of our new chiral auxiliary, and reported syntheses of variety kinds of optical active aryl methanol and diary methanol, using the chiral auxiliary. We also focused on 4-butylphthalide known as a major fragrance of celery oil determined whose research started in 1890's. The absolute configuration of 4-butylphthalide has been speculated by the mechanism of asymmetric synthesis. The structure of the fragrance was finally determined as (S)-(-)-4-butylphthalide. We also succeeded in the synthesis of two enantiomers of the fragrance of matsutake mushroom known as "matsutakeol".It is well known that enantioresolution of alcohols with aliphatic long-chaine and the determination of absolute configuration of the hydroxyl groups is difficult. There has been also no report of asymmetric synthesis of such alcohols. We, recently, succeeded in the enantioresolution of such alcohols with 36 carbons prepared from oleic acid and determination of absolute configuration of its hydroxyl group. This is a promising methodology to synthesis of biological active alcohols consists of long-chain aliphatic substituents.