Annulation cascade of arylnitriles with alkynes to stable delocalized PAH carbocations via intramolecular rhodium migration†,Chemical Science

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Annulation cascade of arylnitriles with alkynes to stable delocalized PAH carbocations via intramolecular rhodium migration†
Chemical Science ( IF 7.6 ) Pub Date : 2018-05-29 00:00:00 , DOI: 10.1039/c8sc01963k
Jiangliang Yin ₁ , Fulin Zhou ₁ , Lei Zhu ₂ , Mufan Yang ₁ , Yu Lan ₂ , Jingsong You ₁

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Herein, we propose the conception of heteroatom-promoted delocalization of the positive charge of an oxonium ion and thus develop a highly efficient rhodium(III)-catalyzed hydration and three fold C–H activation/annulation cascade of arylnitriles with alkynes, affording a structurally diverse family of delocalized polycyclic aromatic hydrocarbon (PAH) carbocations. DFT calculations demonstrate that the positive charge mostly locates around the C1 atom and is partly delocalized by ambient N, O1 and C5 atoms. A mechanistic study indicates that the hydration of the arylnitrile and three fold insertion of the alkyne is a successive process rather than a step by step process, wherein a unique intramolecular rhodium migration is probably involved. These novel carbeniums show tunable fluorescence emission, low cytotoxicity and the ability to specifically target lysosomes.

中文翻译：

芳腈与炔烃的环化级联通过分子内铑迁移形成稳定的离域 PAH 碳阳离子†

在此，我们提出了杂原子促进氧鎓离子正电荷离域的概念，从而开发了一种高效的铑（III) 催化的水合和芳腈与炔烃的三倍 C-H 活化/环化级联，提供结构多样的离域多环芳烃 (PAH) 碳阳离子家族。DFT 计算表明，正电荷主要位于 C1 原子周围，部分被环境 N、O1 和 C5 原子离域。机理研究表明，芳腈的水合和炔烃的三重插入是一个连续的过程，而不是一个逐步的过程，其中可能涉及独特的分子内铑迁移。这些新型碳鎓显示出可调谐的荧光发射、低细胞毒性和特异性靶向溶酶体的能力。

更新日期：2018-05-29

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