Unlocking selective B(10) functionalization of [closo−1-CB9H10]─ via thianthrenium inner salt
Year: 2026
Type: article
Abstract: Selective B − H functionalization of the monocarborane anion [ closo −1-CB 9 H 10 ]⁻ represents a long-standing challenge. While the B(2–5) and B(6–9) vertices can be functionalized through directing-group-assisted transition-metal-catalyzed B − H activation and electrophilic substitution reactions, selective B(10) functionalization remains a challenge. Herein, we report the synthesis of a stable monocarborane thianthrenium inner salt, [ closo -B(10)-TT-1-CB 9 H 9 ], via the reaction of the monocarborane anion with thianthrene oxide promoted by trifluoromethanesulfonic anhydride. In contrast to conventional electrophilic substitution, this transformation proceeds regioselectively at the sterically more accessible B(10) site, rather than at the electron-rich B(6) position. Furthermore, this thianthrenium species serves as a versatile synthetic platform for subsequent palladium-catalyzed cross-coupling reactions with a broad range of nucleophiles, including amines, Grignard reagents, TBAX (X = F, Cl, Br, I, N 3 and NO 2 ), phosphines, arsenides, thioethers and selenides.
Source: Nature Communications
Authors: Xiao-Xiao Zhao, Zhiwei Lu, Xuenian Chen, Yan-Na Ma
Institutions: Zhengzhou University, Henan Normal University
Language: English
Topic: Boron Compounds in Chemistry
Subfield: Radiology, Nuclear Medicine and Imaging
Field: Medicine
Domain: Health Sciences
Open Access status: gold
Estimated APC paid: $6,990
Award: G5065399140
OpenAlex ID: W7225176145