Enantioselective Synthesis of Spirosilabicyclohexenes by Asymmetric Dual Ring Expansion of Spirosilabicyclobutane with Alkynes
Enantioselective Synthesis of Spirosilabicyclohexenes by Asymmetric Dual Ring Expansion of Spirosilabicyclobutane with Alkynes
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DOI：
10.1002/anie.202212889
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发表时间：
2022-10-26
影响因子：
16.6
通讯作者：
Song, Zhenlei
中科院分区：
文献类型：
--
作者：
Chen, Hua;Peng, Ju;Song, Zhenlei
螺硅烷由于其手性螺硅中心而引起了人们的特别关注，该中心作为理想的碳等排体，可以赋予螺类似物独特的性质。不同于以前报道的环化或环加成策略，形成5/5-硅螺环，我们在此报告的不对称双环扩展螺硅双环丁烷与炔合成轴向手性螺硅双环己烯轴承一个新的6/6-硅螺环骨架。密度泛函理论（DFT）计算提供了深入了解的起源，高对映体选择性控制的空间要求的联萘亚磷酰胺配体。手性性质的初步研究表明，螺硅双环己烯类似物之一，具有荧光发射，棉花效应和CPL（圆偏振发光）的活动。
Silaspiranes have attracted particular attention due to their chiral spiro-silicon center, which serves as an ideal carbon isostere and can endow spiro-analogs with distinct properties. Distinct from previously reported cyclization or cycloaddition strategies to form 5/5-silaspiranes, we report herein the asymmetric dual ring expansion of spirosilabicyclobutanes with alkynes to synthesize axially chiral spirosilabicyclohexenes bearing a novel 6/6-silaspirane framework. DFT (density functional theory) calculations provide the deep insight into the origin of the high enantioselectivity controlled by the sterically demanding binaphthyl phosphoramidite ligand. Preliminary studies of chiroptical properties indicate that one of the spirosilabicyclohexene analogs exhibit fluorescence emission, Cotton effects and CPL (circularly polarized luminescence) activity.