Room Temperature Fluoranthene Synthesis through Cationic Rh(I)/H8-BINAP-Catalyzed [2 + 2 + 2] Cycloaddition: Unexpected Acceleration due to Noncovalent Interactions,ACS Catalysis

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Room Temperature Fluoranthene Synthesis through Cationic Rh(I)/H8-BINAP-Catalyzed [2 + 2 + 2] Cycloaddition: Unexpected Acceleration due to Noncovalent Interactions
ACS Catalysis ( IF 11.3 ) Pub Date : 2023-01-12 , DOI: 10.1021/acscatal.2c05683
Ryota Abe ₁ , Yuki Nagashima ₁ , Jin Tanaka ₁ , Ken Tanaka ₁

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The fluoranthene skeleton is a structure often found in natural products and fluorescent materials, and thus developing an operationally simple method for diversity-oriented fluoranthene synthesis is an important research topic in organic synthesis. However, existing synthetic methods require harsh reaction conditions or limited substrate applicability or both. Here, we report the room temperature synthesis of substituted fluoranthenes and azafluoranthenes through the cationic Rh(I)/H₈-BINAP complex-catalyzed [2 + 2 + 2] cycloaddition using 1,8-dialkynylnaphthalenes. DFT calculations reveal that the H₈-BINAP ligand stabilizes the intermediates, allowing the room temperature reaction. Among the substrates examined, 1,8-bis(phenylethynyl)naphthalene and diarylacetylenes show high reactivity, contrary to the reactivity predicted by their steric bulkiness. Theoretical and experimental mechanistic studies have demonstrated that the noncovalent interactions of the phenyl groups on both the substrates and the ligand accelerate the present sterically demanding reactions by stabilizing the transition states rather than inducing steric repulsions.

中文翻译：

通过阳离子 Rh(I)/H8-BINAP 催化的 [2 + 2 + 2] 环加成室温合成荧蒽：非共价相互作用导致的意外加速

荧蒽骨架是一种常见于天然产物和荧光材料中的结构，因此开发一种操作简单的面向多样性的荧蒽合成方法是有机合成中的一个重要研究课题。然而，现有的合成方法需要苛刻的反应条件或有限的底物适用性或两者兼而有之。_{在这里，我们报告了使用 1,8-二炔基萘通过阳离子 Rh(I)/H 8} -BINAP 络合物催化的 [2 + 2 + 2] 环加成在室温下合成取代荧蒽和氮杂荧蒽。DFT计算表明H ₈-BINAP 配体稳定中间体，允许室温反应。在检查的底物中，1,8-双（苯乙炔基）萘和二芳基乙炔显示出高反应性，这与其空间体积所预测的反应性相反。理论和实验机理研究表明，苯基在底物和配体上的非共价相互作用通过稳定过渡态而不是诱导空间排斥来加速目前的空间要求高的反应。

更新日期：2023-01-12

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