阳离子重排的计算与综合研究在扬琴三萜类化合物的假定生物合成中。
Computational and Synthetic Investigation of Cationic Rearrangement in the Putative Biosynthesis of Justicane Triterpenoids.
机构信息
Department of Chemistry, Yale University, 225 Prospect Street, PO Box 20817, New Haven, CT, 06511, USA.
出版信息
Angew Chem Int Ed Engl. 2019 Jan 21;58(4):1025-1029. doi: 10.1002/anie.201810566. Epub 2018 Dec 21.
Abstract
A biomimetic cationic structural rearrangement of the oleanolic acid framework is reported for the gram-scale synthesis and structural reassignment of justicioside E aglycone. The mechanism of the putative biosynthetic rearrangement is investigated with kinetic, computational, and synthetic approaches. The precursor to rearrangement was accessed through two strategic advancements: (1) synthesis of a 1,3-diketone via oxidation of a β-silyl enone, and (2) diastereoselective 1,3-diketone reduction to form a syn-1,3-diol using SmI with PhSH as a key additive.
摘要
本文报道了齐墩果酸骨架的仿生阳离子结构重排，用于大规模合成和结构重分配苷元 jusiticoside E。通过动力学、计算和合成方法研究了假定的生物合成重排的机制。通过两种策略进展来获得重排前体：(1) 通过β-硅烯酮的氧化合成 1,3-二酮，和(2) 使用 SmI 并以 PhSH 作为关键添加剂进行立体选择性 1,3-二酮还原形成顺式-1,3-二醇。
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