Nakai Masaaki, Kageyama Norihiko, Nakahara Koichi, Miki Wataru
Suntory Research Center, Suntory Ltd, Osaka, Japan.
Biosci Biotechnol Biochem. 2006 May;70(5):1273-6. doi: 10.1271/bbb.70.1273.
The methylenedioxyphenyl moiety in the structure of sesamin and episesamin was changed into the catechol moieties, (1R,2S,5R,6S)-6-(3,4-dihydroxyphenyl)-2-(3,4-methylenedioxyphenyl)-3,7-dioxabicyclo[3,3,0]octane, (1R,2R,5R,6S)-2-(3,4-dihydroxyphenyl)-6-(3,4-methylenedioxyphenyl)-3,7-dioxabicyclo[3,3,0]octane, (1R,2R,5R,6S)-6-(3,4-dihydroxyphenyl)-2-(3,4-methylenedioxyphenyl)-3,7-dioxabicyclo[3,3,0]octane, (1R,2S,5R,6S)-2,6-bis(3,4-dihydroxyphenyl)-3,7-dioxabicyclo[3,3,0]octane, and (1R,2R,5R,6S)-2,6-bis(3,4-dihydroxyphenyl)-3,7-dioxabicyclo[3,3,0]octane, in supercritical water. These products had same structures as the sesamin metabolites which act as antioxidants in the liver. These features suggested the direct preparation of antioxidants from sesamin by a one-step reaction using supercritical water.
芝麻素和表芝麻素结构中的亚甲二氧基苯基部分在超临界水中转化为儿茶酚部分，即(1R,2S,5R,6S)-6-(3,4-二羟基苯基)-2-(3,4-亚甲二氧基苯基)-3,7-二氧杂双环[3,3,0]辛烷、(1R,2R,5R,6S)-2-(3,4-二羟基苯基)-6-(3,4-亚甲二氧基苯基)-3,7-二氧杂双环[3,3,0]辛烷、(1R,2R,5R,6S)-6-(3,4-二羟基苯基)-2-(3,4-亚甲二氧基苯基)-3,7-二氧杂双环[3,3,0]辛烷、(1R,2S,5R,6S)-2,6-双(3,4-二羟基苯基)-3,7-二氧杂双环[3,3,0]辛烷和(1R,2R,5R,6S)-2,6-双(3,4-二羟基苯基)-3,7-二氧杂双环[3,3,0]辛烷。这些产物具有与在肝脏中作为抗氧化剂的芝麻素代谢物相同的结构。这些特征表明可通过使用超临界水的一步反应从芝麻素直接制备抗氧化剂。
