Yan Yu, Wei Qi, Su Zhishan, Hang Nan-Nan, Hayashi Tamio, Ming Jialin
Engineering Research Center of Sichuan-Tibet Traditional Medicinal Plant, College of Chemistry and Chemical Engineering, Chengdu University, Chengdu, China.
Inner Mongolia Key Laboratory of Low Carbon Catalysis, College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot, China.
Nat Commun. 2024 Nov 15;15(1):9915. doi: 10.1038/s41467-024-54241-x.
Carbon-silicon-switch strategy, replacing one specific carbon atom in organic molecules with a silicon, has garnered significant interest for developing new functional molecules. However, the influence of a reaction regarding its selectivity and reactivity by carbon-silicon-switch strategy has far less been investigated. Here we discover an unusual carbon-silicon-switch effect in the enantioselective construction of silicon-stereogenic center. It is found that there has been a significant change in the desymmetrization reaction of silacyclohexadienones using asymmetric conjugate addition or oxidative Heck reaction with aryl/alkyl nucleophiles when compared with their carbon analogues cyclohexadienones. Specifically, the carbon-silicon-switch leads to a reversal in enantioselectivity with arylzinc as the nucleophile by the same chiral catalyst, and results in totally different reactivity with arylboronic acid as the nucleophile. Control experiments and density functional theory (DFT) calculations have shown that the unusual carbon-silicon-switch effect comes from the unique stereoelectronic feature of silicon.
碳 - 硅交换策略，即将有机分子中的一个特定碳原子用硅原子取代，在开发新型功能分子方面引起了广泛关注。然而，关于碳 - 硅交换策略对反应选择性和反应性的影响，目前的研究还非常少。在此，我们发现在硅立体中心的对映选择性构建中存在一种不寻常的碳 - 硅交换效应。研究发现，与它们的碳类似物环己二烯酮相比，硅杂环己二烯酮在使用不对称共轭加成或与芳基/烷基亲核试剂进行氧化Heck反应时的去对称化反应有显著变化。具体而言，碳 - 硅交换导致在相同手性催化剂作用下，以芳基锌作为亲核试剂时对映选择性发生反转，并且以芳基硼酸作为亲核试剂时反应性完全不同。对照实验和密度泛函理论（DFT）计算表明，这种不寻常的碳 - 硅交换效应源于硅独特的立体电子特性。
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