Lewis Acid-Catalyzed Selective [2 + 2]-Cycloaddition and Dearomatizing Cascade Reaction of Aryl Alkynes with Acrylates,Journal of the American Chemical Society

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Lewis Acid-Catalyzed Selective [2 + 2]-Cycloaddition and Dearomatizing Cascade Reaction of Aryl Alkynes with Acrylates
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2017-09-18 00:00:00 , DOI: 10.1021/jacs.7b07997
Liang Shen ₁ , Kai Zhao _{1,

2} , Kazuki Doitomi ₃ , Rakesh Ganguly ₁ , Yong-Xin Li ₁ , Zhi-Liang Shen _{1,

2} , Hajime Hirao _{1,

3} , Teck-Peng Loh _{1,

2}

Affiliation

Combined Lewis acid, consisting of two or more Lewis acids, sometimes shows unique catalytic ability, and it may promote reactions which could not be catalyzed by any of the Lewis acids solely. On the other hand, the development of efficient methods for the facile synthesis of cyclobutenes and densely functionalized decalins is an attractive target for synthetic chemists due to their versatile synthetic utilities and widespread occurrence in natural products. Herein, we wish to report an efficient method for the assembly of cyclobutenes and densely functionalized decalin skeletons through In(tfacac)₃-TMSBr catalyzed selective [2 + 2]-cycloaddition and dearomatizing cascade reaction of aryl alkynes with acrylates with high chemo- and stereoselectivity. The obtained cyclobutene could be easily converted into cyclobutane as well as synthetically useful 1,4- and 1,5-diketones with high chemo- and stereoselectivity. On the basis of mechanistic studies, plausible reaction mechanisms were proposed for both the [2 + 2]-cycloaddition and the dearomatizing cascade reaction. Finally, the computational studies of reaction mechanisms were conducted, and the results suggest that the combined Lewis acid could efficiently promote both reactions.

中文翻译：

Lewis酸催化芳烃炔烃与丙烯酸酯的选择性[2 + 2]-环加成反应和脱芳香化级联反应

由两种或多种路易斯酸组成的组合路易斯酸有时会显示出独特的催化能力，并且它可能会促进仅由任何一种路易斯酸都无法催化的反应。另一方面，由于其通用的合成用途和在天然产物中的广泛应用，开发用于合成环丁烯和致密官能化十氢化萘的有效方法是合成化学家的一个有吸引力的目标。在此，我们希望报告一种通过In（tfacac）₃组装环丁烯和密集官能化十氢萘骨架的有效方法-TMSBr催化具有高化学和立体选择性的芳基炔烃与丙烯酸酯的选择性[2 + 2]-环加成反应和脱芳烃级联反应。所获得的环丁烯可以容易地转化成环丁烷以及合成上有用的具有高化学和立体选择性的1，4-和1，5-二酮。在机理研究的基础上，提出了[2 + 2]-环加成反应和脱芳香化级联反应的合理反应机理。最后，对反应机理进行了计算研究，结果表明结合的路易斯酸可以有效地促进两个反应。

更新日期：2017-09-19

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