Sulake Rohidas S, Jiang Yan-Feng, Lin Hsiao-Han, Chen Chinpiao
Department of Chemistry, National Dong-Hwa University , Hualien 97401, Taiwan.
J Org Chem. 2014 Nov 21;79(22):10820-8. doi: 10.1021/jo501735z. Epub 2014 Nov 6.
Total synthesis of (±)-antroquinonol D, which is isolated from very expensive and rarely found Antrodia camphorata and which has potential anticancer properties, was achieved from 4-methoxyphenol. In addition, a Michael addition to dimethoxy cyclohexadienones was studied. The main step involved chelation and substrate-controlled diastereoselective reduction of cyclohexenone and lactonization. Lactone synthesis facilitated the diastereoselective reduction of ketone, which help control the desired stereochemistry at the crucial stereogenic center in the natural product. Other key reactions in the synthesis involved a Michael addition of dimethyl malonate on cyclohexadienone, dihydroxylation, and Wittig olefination. A sesquiterpene side chain was synthesized through coupling with geranyl phenyl sulfide and Bouveault-Blanc reduction.
从非常昂贵且罕见的樟芝中分离得到的具有潜在抗癌特性的（±）-樟芝醌醇D，以4-甲氧基苯酚为原料实现了全合成。此外，还研究了对二甲氧基环己二烯酮的迈克尔加成反应。主要步骤包括螯合以及环己烯酮的底物控制非对映选择性还原和内酯化反应。内酯合成促进了酮的非对映选择性还原，这有助于控制天然产物关键手性中心处所需的立体化学。合成中的其他关键反应包括丙二酸二甲酯对环己二烯酮的迈克尔加成、二羟基化反应和维蒂希烯烃化反应。通过与香叶基苯硫醚偶联和布沃-布朗还原反应合成了一个倍半萜侧链。
