对映体纯1-甲基-7-氧杂双环[2.2.1]庚烷-2-酮的制备  

Preparation of Enantiomerically Pure 1-Methyl-7-oxabicyclo[2.2.1]heptan-2-one

作　　者：关玉昆[1] 房丽晶[1] 郑国君[1] 李裕林[1] 

机构地区：[1]兰州大学功能有机分子化学国家重点实验室,有机化学研究所兰州730000

出　　处：《高等学校化学学报》2005年第2期264-266,共3页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金 (批准号 :2 0 2 72 0 2 1)资助

摘　　要：(±)-1-Methyl-7-oxabicyclo[2.2.1]heptan-2-one (1) is a versatile chiral building block for terpenoids. It could be applied in total synthesis of eudesmanes, agarofurans and norcarotenoids. Compound (±)-1 was reduced to alcohol (±)-2. Compound (±)-2 was esterified with commercial available optically pure (S)-(+)-mandelic acid. The diastereomeric ester mixture was separated with preparative HPLC method. After oxidation of the saponified products of diastereomeric ester (+)-4 and (+)-5 respectively, both optically pure enantiomers of compound 1 were prepared for the first time in four steps with an overall yield of 70%. The absolute configurations of (+)-1 and (-)-1 were determined as (+)-(1R,4S)-1-methyl-7-oxabicyclo[2.2.1] heptan-2-one and (-)-(1S,4R)-1-methyl-7-oxabicyclo[2.2.1] heptan-2-one.(±)-1-Methyl-7-oxabicyclo[2.2.1]heptan-2-one (1) is a versatile chiral building block for terpenoids. It could be applied in total synthesis of eudesmanes, agarofurans and norcarotenoids. Compound (±)-1 was reduced to alcohol (±)-2. Compound (±)-2 was esterified with commercial available optically pure (S)-(+)-mandelic acid. The diastereomeric ester mixture was separated with preparative HPLC method. After oxidation of the saponified products of diastereomeric ester (+)-4 and (+)-5 respectively, both optically pure enantiomers of compound 1 were prepared for the first time in four steps with an overall yield of 70%. The absolute configurations of (+)-1 and (-)-1 were determined as (+)-(1R,4S)-1-methyl-7-oxabicyclo[2.2.1] heptan-2-one and (-)-(1S,4R)-1-methyl-7-oxabicyclo[2.2.1] heptan-2-one.

关 键 词：1-甲基-7-氧杂双环[2.2.1]庚烷-2-酮 萜类化合物 扁桃酸 拆分 

分 类 号：O621[理学—有机化学]