Enantioresolution of Alcohols and its Application to Organic Synthesis

(S)-(+)-2-甲氧基-2-（1-萘基）丙酸，即(S)-(+)- m - α np酸，是由Nobuyuki Harada教授，shunsike Kuwahara博士和我共同设计的，有两个作用；一种是仲醇的非对映体分离，另一种是醇羟基绝对构型的同时测定。我们关注了新手性助剂的这些作用，并报道了用该手性助剂合成了多种光学活性芳基甲醇和日记甲醇。我们还专注于4-丁苯酞，这是芹菜油的主要香料，其研究始于1890年代。利用不对称合成机理推测了4-丁苯酞的绝对构型。最终确定香精的结构为(S)-(-)-4-丁苯酞。我们还成功合成了两种松茸香精对映体，称为“松茸醇”。众所周知，具有脂肪族长链的醇的对映体拆分和羟基绝对构型的确定是困难的。也没有不对称合成这类醇的报道。最近，我们成功地对由油酸制备的36个碳的醇进行了对映分辨，并测定了其羟基的绝对构型。这是一种很有前途的合成长链脂肪取代基生物活性醇的方法。

(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.