从兰科千里光属植物中分离得到的高度含氧倍半萜类化合物的全合成：天然产物的相对和绝对构型。

Total Synthesis of Highly Oxygenated Bisabolane Sesquiterpene Isolated from Ligularia lankongensis: Relative and Absolute Configurations of the Natural Product.

机构信息

Graduate School of Pharmaceutical Sciences, Meiji Pharmaceutical University , 2-522-1 Noshio, Kiyose, Tokyo 204-8588, Japan.

Department of Chemistry, Rikkyo University , 3-34-1 Nishi-Ikebukuro, Toshima-ku, Tokyo 171-8501, Japan.

出版信息

J Org Chem. 2018 Jan 19;83(2):703-715. doi: 10.1021/acs.joc.7b02688. Epub 2018 Jan 8.

DOI:10.1021/acs.joc.7b02688

PMID:29282987

Abstract

The relative and absolute configurations of an oxygenated bisabolane natural product, isolated from Ligularia lankongensis, were determined by synthesis. All four possible stereoisomers and their tiglate analogues were synthesized from R-(-)-carvone, and their H and C NMR spectra were compared to establish the 6R,8S,10S configuration. The stereoselective synthesis of the natural product was also achieved, featuring Brown allylation, vanadium-catalyzed epoxidation, and the Mitsunobu reaction.

摘要

从兰钟花属 Ligularia lankongensis 中分离出的含氧双环大牻牛儿烷天然产物，通过合成确定了其相对和绝对构型。从 R-(-)-香芹酮合成了所有四个可能的立体异构体及其惕各酸酯类似物，并比较了它们的 H 和 C NMR 谱，以确定 6R,8S,10S 的构型。还通过布朗烯丙基化、钒催化环氧化和 Mitsunobu 反应实现了天然产物的立体选择性合成。