Catalytic Asymmetric Deoxygenative Cyclopropanation Reactions by a Chiral Salen-Mo Catalyst,Journal of the American Chemical Society

当前位置： X-MOL 学术 › J. Am. Chem. Soc. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

Catalytic Asymmetric Deoxygenative Cyclopropanation Reactions by a Chiral Salen-Mo Catalyst
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-01-10 , DOI: 10.1021/jacs.2c12225
Li-Ya Cao ₁ , Jia-Le Wang ₁ , Kai Wang ₁ , Jiang-Bin Wu ₁ , De-Ku Wang ₁ , Jia-Min Peng ₁ , Jin Bai ₁ , Chun-Xiang Zhuo ₁

Affiliation

The catalytic asymmetric cyclopropanation reaction of alkenes with diazo compounds is a direct and powerful method to construct chiral cyclopropanes that are essential to drug discovery. However, diazo compounds are potentially explosive and often require hazardous reagents for their preparation. Here, we report on the use of 1,2-dicarbonyl compounds as safe and readily available surrogates for diazo compounds in the direct catalytic asymmetric deoxygenative cyclopropanation reaction. Enabled by a class of simple and readily accessible chiral salen-Mo catalysts, the reaction proceeded with generally good enantioselectivities and yields toward a wide range of substrates (80 examples). Preliminary mechanistic studies suggested that the proposed μ-oxo bridged dinuclear Mo(III)-species was the catalytically active species. This strategy not only provides a promising route for the synthesis of chiral cyclopropanes but also opens a new window for the potential applications of chiral salen-Mo complexes in asymmetric catalysis.

中文翻译：

手性 Salen-Mo 催化剂催化不对称脱氧环丙烷化反应

烯烃与重氮化合物的催化不对称环丙烷化反应是构建对药物发现至关重要的手性环丙烷的直接而有效的方法。然而，重氮化合物具有潜在的爆炸性并且通常需要危险的试剂来制备它们。在这里，我们报告了在直接催化不对称脱氧环丙烷化反应中使用 1,2-二羰基化合物作为重氮化合物的安全且容易获得的替代物。在一类简单且易于获得的手性 salen-Mo 催化剂的支持下，该反应通常具有良好的对映选择性，并且对广泛的底物（80 个例子）具有良好的产率。初步的机理研究表明，拟议的 μ-氧代桥联双核 Mo(III) 物种是催化活性物种。

更新日期：2023-01-10

点击分享查看原文

点击收藏

阅读更多本刊新发论文本刊介绍/投稿指南