Molybdenum-Catalyzed Deoxygenative Cyclopropanation of 1,2-Dicarbonyl or Monocarbonyl Compounds,Angewandte Chemie International Edition

当前位置： X-MOL 学术 › Angew. Chem. Int. Ed. › 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.)

Molybdenum-Catalyzed Deoxygenative Cyclopropanation of 1,2-Dicarbonyl or Monocarbonyl Compounds
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2021-04-26 , DOI: 10.1002/anie.202103429
Li-Ya Cao ₁ , Jian-Nan Luo ₁ , Jia-Sheng Yao ₁ , De-Ku Wang ₁ , Yuan-Qing Dong ₁ , Chao Zheng ₂ , Chun-Xiang Zhuo ₁

Affiliation

The transition-metal-catalyzed cyclopropanation of alkenes by the decomposition of diazo compounds is a powerful and straightforward strategy to produce cyclopropanes, but is tempered by the potentially explosive nature of diazo substrates. Herein we report the Mo-catalyzed regiospecific deoxygenative cyclopropanation of readily available and bench-stable 1,2-dicarbonyl compounds, in which one of the two carbonyl groups acts as a carbene equivalent upon deoxygenation and engages in the subsequent cyclopropanation process. The use of a commercially available Mo catalyst afforded an array of valuable cyclopropanes with exclusive regioselectivity in up to 90 % yield. The synthetic utility of this method was further demonstrated by gram-scale syntheses, late-stage functionalization, and the cyclopropanation of a simple monocarbonyl compound. Preliminary mechanistic studies suggest that phosphine (or silane) acts as both a mild reductant and a good oxygen acceptor that efficiently regenerates the catalytically active Mo catalyst through reduction of the Mo-oxo complexes.

中文翻译：

钼催化的 1,2-二羰基或单羰基化合物的脱氧环丙烷化

通过重氮化合物的分解，过渡金属催化的烯烃环丙烷化是一种强大而直接的生产环丙烷的策略，但受到重氮底物潜在爆炸性的影响。在此，我们报告了 Mo 催化的易得且实验室稳定的 1,2-二羰基化合物的区域特异性脱氧环丙烷化，其中两个羰基之一在脱氧时充当卡宾等价物，并参与随后的环丙烷化过程。使用市售的 Mo 催化剂提供了一系列有价值的环丙烷，具有独特的区域选择性，产率高达 90%。该方法的合成效用通过克级合成、后期功能化和简单单羰基化合物的环丙烷化得到进一步证明。

更新日期：2021-06-28

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