通过芳香族B-H键断裂一锅法合成联芳基稠合单碳-闭式十二硼酸盐

One-pot Annulation for Biaryl-fused Monocarba-closo-dodecaborate through Aromatic B-H Bond Disconnection.

作者信息

Akimoto Gaku, Otsuka Mai, Miyamoto Kazunori, Muranaka Atsuya, Hashizume Daisuke, Takita Ryo, Uchiyama Masanobu

机构信息

Graduate School of Pharmaceutical Sciences, The University of Tokyo, 7-3-1 Hongo, Bunkyo-ku, Tokyo, 113-0033, Japan.

Advanced Elements Chemistry Research Team, RIKEN Center for Sustainable Resource Science, and Elements Chemistry Laboratory, RIKEN, 2-1 Hirosawa, Wako-shi, Saitama, 351-0198, Japan.

出版信息

Chem Asian J. 2018 Apr 16;13(8):913-917. doi: 10.1002/asia.201800053. Epub 2018 Mar 13.

DOI:10.1002/asia.201800053

PMID:29488692

Abstract

We have developed a one-pot annulation reaction of monocarba-closo-dodecaborate with cyclic diaryliodonium salts to afford biaryl-fused derivatives. Aryl functionalities are introduced at both the 1-carbon and unreactive ortho-boron vertices of the "σ-aromatic" carborane cage without the need for pre-functionalization. DFT calculations revealed that the palladium-catalyzed C-B bond-formation step in this process proceeds through a concerted metalation-deprotonation (CMD)-type pathway for the B-H bond disconnection on the aromatic cage, though such bonds are generally regarded as hydridic.

摘要

我们已经开发出一种单锅法，使单碳-闭式-十二硼酸盐与环状二芳基碘鎓盐发生环化反应，以得到联芳基稠合衍生物。芳基官能团被引入到“σ-芳香性”碳硼烷笼的1-碳和无反应性的邻位硼顶点上，而无需预先官能化。密度泛函理论计算表明，在此过程中钯催化的C-B键形成步骤通过协同金属化-去质子化（CMD）型途径进行，以断开芳香笼上的B-H键，尽管此类键通常被认为具有氢化物性质。