Scalable Synthesis of Vicinal Quaternary Stereocenters via the Solid-State Photodecarbonylation of a Crystalline Hexasubstituted Ketone
Scalable Synthesis of Vicinal Quaternary Stereocenters via the Solid-State Photodecarbonylation of a Crystalline Hexasubstituted Ketone
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DOI：
10.1021/acs.orglett.0c03226
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发表时间：
2020-11-20
期刊：
影响因子：
5.2
通讯作者：
Garcia-Garibay, Miguel A.
中科院分区：
文献类型：
--
作者：
Chang, Trevor Y.;Dotson, Jordan J.;Garcia-Garibay, Miguel A.
我们报道了一个六取代酮的合成和立体定向固态光脱羰反应，该酮具有六个不同的α-取代基。固态转化的光产物具有邻位全碳四元立构中心的特征。虽然在散装粉末和含水结晶悬浮液中进行的反应由于初级光产物的二次光化学而变得复杂，但最佳条件提供了良好的产率和可回收的起始材料。具有正交化学反应性的α-取代基的后续转化说明了这种转化朝向构建复杂结构的潜力。
We report the synthesis and stereospecific solid-state photodecarbonylation of a hexasubstituted ketone featuring six distinct alpha-substituents. The photoproduct of the solid-state transformation features vicinal all-carbon quaternary stereocenters. While reactions carried out in bulk powders and aqueous crystalline suspensions were complicated by secondary photochemistry of the primary photoproduct, optimal conditions provided good yields and recyclable starting material. Subsequent transformations of the alpha-substituents having orthogonal chemical reactivity illustrate the potential of this transformation toward constructing complex architectures.