Unraveling the C−H Arylation of Benzo‐Fused Cycloalkanones: Combined Experimental and Computational Evidence,Advanced Synthesis & Catalysis

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Unraveling the C−H Arylation of Benzo‐Fused Cycloalkanones: Combined Experimental and Computational Evidence
Advanced Synthesis & Catalysis ( IF 4.4 ) Pub Date : 2021-01-20 , DOI: 10.1002/adsc.202001349
Benjamin Large ₁ , Damien PRIM ₂

Affiliation

The C−H functionalization of benzo‐fused cycloalkanones represents a synthetic challenge, since such scaffolds display different activation sites, at sp² and sp³ carbons, a bicyclic structure, and various sizes of the cycloalkanone ring. Anticipating the outcome of C−H functionalization and the impact of the presence and size of the cycloalkanone ring would help to foresee synthetic routes to more complex molecular architectures. The mechanism of C−H arylation was studied using DFT calculations for tetralone, benzosuberone, and indanone and compared to acetophenone. Comparison of energetic profiles allowed identifying key steps of the process. Analysis of the topology of key intermediates allowed correlating the deformation of palladacycles to the potential reactivity of the benzo‐fused cycloalkanone family members. The experimental results were in full agreement with the trend provided by the theoretical study. A wide panel of diversely substituted benzo‐fused cycloalkanones has been successfully obtained using optimized conditions. Moreover, an approach towards polycyclic molecules has been illustrated featuring a C−H arylation and a second step taking advantage of the remaining ketone fragment and its ability to undergo diverse transformations leading to alternative pathways to more complex molecular architectures

中文翻译：

分解苯并环烷烃的CH芳基化：结合实验和计算证据

苯并稠合环烷酮的CH官能化代表了一项合成挑战，因为此类支架在sp ²和sp ³处显示出不同的激活位点碳，双环结构和各种尺寸的环烷酮环。预期CH功能化的结果以及环烷酮环的存在和大小的影响将有助于预见到更复杂分子结构的合成途径。使用DFT计算研究了四氢萘酮，苯并亚砜和茚满酮的CH芳基化机理，并将其与苯乙酮进行了比较。通过比较能量曲线，可以确定过程的关键步骤。通过分析关键中间体的拓扑结构，可以将palladacycles的变形与苯并稠合的环烷酮家族成员的潜在反应性相关联。实验结果与理论研究的趋势完全吻合。在优化条件下，已经成功获得了各种各样的取代苯并稠合的环烷酮。此外，已经说明了一种针对多环分子的方法，该方法具有CH芳基化和第二步，可利用剩余的酮片段及其经历多种转化的能力，从而导致通往更复杂分子结构的替代途径

更新日期：2021-03-16

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