Diastereoselective Total Synthesis of (+/-)-Basiliolide B and (+/-)-epi-8-Basiliolide B
Diastereoselective Total Synthesis of (+/-)-Basiliolide B and (+/-)-epi-8-Basiliolide B
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(/-)-罗勒内酯B和(/-)-epi-8-罗勒内酯B的非对映选择性全合成
DOI：
10.1021/acs.joc.6b02921
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发表时间：
2017
影响因子：
3.6
通讯作者：
Lee Chi-Sing
中科院分区：
文献类型：
--
作者：
Liang Xuefeng;Zhou Liyan;Min Long;Ye Weijian;Bao Wenli;Ma Wenjing;Yang Qianqian;Qiao Fangfang;Zhang Xinhao;Lee Chi-Sing
的C8和C9立体异构中心的basiliprimidine/transstaganiprimidine家庭已建立立体选择性使用环丙烷开环策略，这已通过DFT计算的各种锂螯合模型进行了研究。在此策略中获得的高度官能化的中间体被成功地用于非对映选择性全合成（±）-basiliperine B和（±）-epi-8-basiliperine B。通过2-吡喃酮的Diels-Alder（DA）环加成反应构建了具有内酯桥的十氢萘核，并通过仿生分子内O-酰化环化反应得到了前所未有的七元酰基烯酮缩醛.
The C8 and C9 stereogenic centers of the basiliolide/transtaganolide family have been established stereoselectively using a cyclopropane ring-opening strategy, which has been studied by DFT calculations of a variety of lithium-chelating models. The highly functionalized intermediates obtained in this strategy were successfully employed for the diastereoselective total synthesis of (±)-basiliolide B and (±)-epi-8-basiliolide B. The decalin core with a lactone bridge was constructed via a 2-pyrone Diels–Alder (DA) cycloaddition, and the unprecedented seven-membered acyl ketene acetal was established by a biomimetic intramolecularO-acylation cyclization.