对称化
全合成
天然产物
立体化学
化学
烯丙基重排
戒指(化学)
亚科
对映选择合成
分子内力
双功能
对映体
有机化学
生物化学
基因
催化作用
作者
Leo Betschart,Karl‐Heinz Altmann
标识
DOI:10.1002/anie.202315423
摘要
Isoxeniolide A is a highly strained xenicane diterpenoid of marine origin. This natural product is representative for a subfamily of xenicanes incorporating an allylic hydroxy group in the nine-membered ring; members of this xenicane subfamily so far have not been targeted by total synthesis. Herein, we describe the first asymmetric total synthesis of isoxeniolide A. Key to forming the challenging E-configured cyclononene ring was a diastereoselective intramolecular Nozaki-Hiyama-Kishi reaction. Other important transformations include an enzymatic desymmetrization for absolute stereocontrol, a diastereoselective cuprate addition and the use of a bifunctional vinyl silane building block. Our strategy also permits access to the enantiomer of the natural product and holds potential to access a multitude of xenicane natural products and analogs for structure-activity relationship studies.
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