|
|||||
|
|
One‐pot Annulation for Biaryl‐fused Monocarba‐closo‐dodecaborate through Aromatic B−H Bond Disconnection |
|
| Authors: | Gaku Akimoto Mai Otsuka Dr Kazunori Miyamoto Dr Atsuya Muranaka Dr Daisuke Hashizume Dr Ryo Takita Prof?Dr Masanobu Uchiyama |
| Affiliation: | 1. Graduate School of Pharmaceutical Sciences, The University of Tokyo, Bunkyo-ku, Tokyo, Japan;2. Advanced Elements Chemistry Research Team, RIKEN Center for Sustainable Resource Science, and Elements Chemistry Laboratory, RIKEN, Wako-shi, Saitama, Japan;3. Materials Characterization Support Unit, RIKEN Center for Emergent Matter Science, Wako-shi, Saitama, Japan |
| 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. |
| Keywords: | annulation arylation caborane anion copper palladium |
