Boron-Masking Strategy for New Transformations of Organoboronic Acids

通过缩合在有机硼酸的硼原子上引入“掩蔽基团”，发展了合成高功能化有机硼酸的新方法。1，8-二氨基萘是一种非常强健的保护基团，特别是在铃木。宫仓联轴器。掩蔽基允许通过迭代交叉偶联、迭代合成低聚(苯亚乙叉)S和简单地合成基于低聚芳烃的树枝状化合物来合成低聚芳烃。制备了两个硼原子中的一个被保护的二硼试剂，并将其用于炔基二硼反应，生成了区域选择性的二硼反应产物，适用于逐步交叉偶联反应。2-(吡唑-5-基)苯胺(PZA)和邻氨基苯甲酰胺(AAM)与有机硼酸的缩合物在Ru的催化下发生了硅邻位加成反应，其中的含氮基团(PZA和AAM)作为邻位导向基，反应后很容易被移除。AAM基团还作为铃木中的硼基的保护基团。宫仓联轴器。

New methods for the synthesis of highly functionalized organoboronic acids have been developed on the basis of introduction of "masking groups" onto the boron atoms of organoboronic acids by condensation. 1, 8-Diaminonaphthalene served as a highly robust protecting group particularly in Suzuki. Miyaura coupling. The masking group allowed synthesis of oligoarenes via iterative cross-coupling, iterative synthesis of oligo(phenylene-vinylene) s, and facile synthesis of oligoarene-based dendrons. A diboron reagent in which one of the two boron atoms is protected has been prepared and used in the alkyne diboration reaction, leading to regioselective formation of diboration products, which were applicable to stepwise cross-coupling reactions. Condensates of 2-(pirazol-5-yl) aniline(PZA) and anthranilamide(AAM) with organoboronic acids underwent ruthenium-catalyzed ortho-silylation, in which the nitrogen-containing masking groups(PZA and AAM) served as ortho-directing groups, which are easily removable after the reaction. The AAM group also served as a protecting group for the boronyl group in the Suzuki. Miyaura coupling.