1,2-Azaborine’s Distinct Electronic Structure Unlocks Two New Regioisomeric Building Blocks via Resolution Chemistry,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.)

1,2-Azaborine’s Distinct Electronic Structure Unlocks Two New Regioisomeric Building Blocks via Resolution Chemistry
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-05-13 , DOI: 10.1021/jacs.9b03611
Cameron R McConnell ₁ , Fredrik Haeffner ₁ , Andrew W Baggett ₁ , Shih-Yuan Liu ₁

Affiliation

Two new 1,2-azaborine building blocks that enable the broad diversification of previously not readily accessible C4 and C5 ring positions of the 1,2-azaborine heterocycle are developed. 1,2-Azaborine's distinct electronic structure allowed the resolution of a mixture of C4- and C5-borylated 1,2-azaborines. The connection between the electronic structure of C4 and C5 positions of 1,2-azaborine and their distinct reactivity patterns is revealed by a combination of reactivity studies and kinetic measurements that are supported by DFT calculations. Specifically, we show that oxidation by N-methylmorpholine N-oxide (NMO) is selective for the C4-borylated 1,2-azaborine, and the Ir-catalyzed deborylation is selective for the C5-borylated 1,2-azaborine via kinetically controlled processes. On the other hand, ligand exchange with diethanolamine takes place selectively with the C4-borylated isomer via a thermodynamically controlled process. These results represent the first examples for chemically distinguishing a mixture of two aryl mono-Bpin-substituted isomers.

中文翻译：

1,2-Azaborine 独特的电子结构通过拆分化学解锁了两个新的区域异构构件

开发了两种新的 1,2-氮杂硼烷结构单元，使以前不易获得的 1,2-氮杂硼烷杂环的 C4 和 C5 环位置广泛多样化。1,2-Azaborine 独特的电子结构允许对 C4-和 C5-硼化 1,2-azaborine 的混合物进行拆分。通过 DFT 计算支持的反应性研究和动力学测量的组合，揭示了 1,2-氮杂硼烷的 C4 和 C5 位置的电子结构与其不同反应性模式之间的联系。具体而言，我们表明 N-甲基吗啉 N-氧化物 (NMO) 的氧化对 C4-硼化 1,2-氮杂硼烷具有选择性，而 Ir 催化的脱硼反应通过动力学控制对 C5-硼化 1,2-氮杂硼烷具有选择性过程。另一方面，与二乙醇胺的配体交换通过热力学控制的过程选择性地与 C4 硼化异构体发生。这些结果代表了化学区分两种芳基单-Bpin 取代异构体的混合物的第一个例子。

更新日期：2019-05-13

点击分享查看原文

点击收藏

公开下载

阅读更多本刊新发论文本刊介绍/投稿指南