Regio- and Stereoselective Transfer Hydrogenation of Aryloxy Group-Substituted Unsymmetrical 1,2-Diketones: Synthetic Applications and Mechanistic Studies,Journal of the American Chemical Society

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Regio- and Stereoselective Transfer Hydrogenation of Aryloxy Group-Substituted Unsymmetrical 1,2-Diketones: Synthetic Applications and Mechanistic Studies
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2024-07-15 , DOI: 10.1021/jacs.4c04171
Wenjun Liu ₁ , Caiyi Ren ₁ , Liyuan Zhou _{1,

2} , Haotian Luo ₁ , Xiangjian Meng ₁ , Peng Luo ₁ , Yingkun Luo ₁ , Wennan Dong ₁ , Shouang Lan ₁ , Jinggong Liu ₃ , Shuang Yang ₁ , Qi Zhang ₄ , Xinqiang Fang ₁

Affiliation

Developing a general method that leads to the formation of different classes of chiral bioactive compounds and their stereoisomers is an attractive but challenging research topic in organic synthesis. Furthermore, despite the great value of asymmetric transfer hydrogenation (ATH) in both organic synthesis and the pharmaceutical industry, the monohydrogenation of unsymmetrical 1,2-diketones remains underdeveloped. Here, we report the aryloxy group-assisted highly regio-, diastereo-, and enantioselective ATH of racemic 1,2-diketones. The work produces a myriad of enantioenriched dihydroxy ketones, and further transformations furnish all eight stereoisomers of diaryl triols, polyphenol, emblirol, and glycerol-type natural products. Mechanistic studies and calculations reveal two working modes of the aryloxy group in switching the regioselectivity from a more reactive carbonyl to a less reactive one, and the potential of ATH on 1,2-diketones in solving challenging synthetic issues has been clearly demonstrated.

中文翻译：

芳氧基取代的不对称 1,2-二酮的区域和立体选择性转移氢化：合成应用和机理研究

开发一种可形成不同类别的手性生物活性化合物及其立体异构体的通用方法是有机合成中一个有吸引力但具有挑战性的研究课题。此外，尽管不对称转移氢化（ATH）在有机合成和制药工业中具有巨大价值，但不对称1,2-二酮的单氢化仍然不发达。在这里，我们报道了外消旋1,2-二酮的芳氧基辅助的高度区域选择性、非对映选择性和对映选择性ATH。这项工作产生了无数对映体富集的二羟基酮，并进一步转化提供了二芳基三醇、多酚、emblirol 和甘油型天然产物的所有八种立体异构体。机理研究和计算揭示了芳氧基将区域选择性从反应性较高的羰基转变为反应性较低的羰基的两种工作模式，并且 ATH 在 1,2-二酮上解决具有挑战性的合成问题的潜力已得到明确证明。

更新日期：2024-07-15

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