一种通往蔷薇烷二萜类化合物立体四元核心的简洁合成路线。
A concise synthetic route to the stereotetrad core of the briarane diterpenoids.
作者信息
Moon Nicholas G, Harned Andrew M
机构信息
†Department of Chemistry, University of Minnesota-Twin Cities, 207 Pleasant Street SE, Minneapolis, Minnesota 55455, United States.
出版信息
Org Lett. 2015 May 1;17(9):2218-21. doi: 10.1021/acs.orglett.5b00816. Epub 2015 Apr 14.
Abstract
A concise synthesis (under 10 steps) of the stereotetrad core of the briarane diterpenoids is reported. This approach harnesses the unique reactivity of salicylate ester derived 2,5-cyclohexadienones to quickly build complexity. In particular, a highly diastereoselective acetylide conjugate addition/β-ketoester alkylation sequence was used to set the relative configuration of the C1 (quaternary) and C10 (tertiary) vicinal stereocenters. The sterochemical outcome of the β-ketoester alkylation appears to be governed by torsional steering in the transition state.
摘要
报道了一种简洁的（少于10步）蔷薇烷二萜类化合物立体四元核心的合成方法。该方法利用水杨酸酯衍生的2,5-环己二烯酮的独特反应性来快速构建复杂性。特别地，采用了高度非对映选择性的乙炔化物共轭加成/β-酮酯烷基化序列来确定C1（季碳）和C10（叔碳）邻位立体中心的相对构型。β-酮酯烷基化的立体化学结果似乎受过渡态中的扭转导向控制。
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