Stereoselective Access to Silicon-Stereogenic Silacycles via the Carbene-Catalyzed Desymmetric Benzoin Reaction of Siladials,ACS Catalysis

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Stereoselective Access to Silicon-Stereogenic Silacycles via the Carbene-Catalyzed Desymmetric Benzoin Reaction of Siladials
ACS Catalysis ( IF 11.3 ) Pub Date : 2022-07-29 , DOI: 10.1021/acscatal.2c02805
Hao Liu ₁ , Pengyu He ₂ , Xuanlong Liao ₁ , Yipeng Zhou ₁ , Xingkuan Chen ₃ , Wenpiao Ou ₃ , Zhenhong Wu ₃ , Cong Luo ₃ , Limin Yang ₂ , Jianfeng Xu ₁

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The catalytic asymmetric synthesis of silicon-stereogenic organosilicon compounds has been a long-standing challenging task and was recently accomplished through a handful of transition-metal-catalyzed approaches. Herein we report an organocatalytic desymmetrization strategy for constructing optically active silicon-stereogenic silacycles. In the presence of a chiral N-heterocyclic carbene (NHC) catalyst, two identical formyl groups on the tetrasubstituted silanes are successfully discriminated to undergo stereoselective intramolecular benzoin reactions, affording enantioenriched dibenzo[b,f]silepin-10-ones featuring carbon- and silicon-stereogenic centers at the 1,4-positions, respectively. This catalytic process can be readily expanded to the gram scale, and the products can be further converted to other valuable molecules. DFT calculations were also conducted to unveil the reaction mechanism and the origins of the stereoselectivities.

中文翻译：

通过 Siladials 的卡宾催化的不对称苯偶姻反应立体选择性获得硅立体 Silacycles

硅立体有机硅化合物的催化不对称合成一直是一项长期具有挑战性的任务，最近通过一些过渡金属催化的方法完成。在这里，我们报告了一种用于构建光学活性硅立体硅环的有机催化去对称化策略。在手性N-杂环卡宾 (NHC) 催化剂存在下，四取代硅烷上的两个相同的甲酰基被成功区分以进行立体选择性的分子内苯偶姻反应，得到对映体富集的二苯并[ b , f] silepin-10-ones 分别在 1,4 位具有碳和硅立体中心。这种催化过程可以很容易地扩展到克级，并且可以将产物进一步转化为其他有价值的分子。还进行了 DFT 计算以揭示反应机理和立体选择性的起源。

更新日期：2022-07-29

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