Li Miaosheng, O'Doherty George A
Department of Chemistry, West Virginia University, Morgantown, West Virginia 26506, USA.
Org Lett. 2006 Dec 21;8(26):6087-90. doi: 10.1021/ol062595u.
[Structure: see text] A de novo approach to the formal total synthesis of the macrolide natural product (-)-apicularen A has been achieved in 18 steps from achiral starting materials. Both the absolute and relative stereochemistries of apicularen A were introduced by a Sharpless asymmetric dihydroxylation, a pi-allyl-palladium catalyzed reduction, a stereoselective reduction, and a base-promoted transannulation to install the C-9 stereocenter.
[结构:见正文] 已从非手性起始原料经18步实现了对大环内酯天然产物(-)-阿皮考林A的形式全合成的从头合成方法。阿皮考林A的绝对和相对立体化学结构通过夏普莱斯不对称双羟基化反应、烯丙基钯催化还原反应、立体选择性还原反应以及碱促进的分子内环化反应引入,以构建C-9立体中心。