期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 142, 期 10, 页码 4586-4591出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.0c00300
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资金
- NIGMS [R35GM124746]
- Research Corporation for Science Advancement (RCSA)
- Majeti-Alapati Fellowship at UCLA
We report the first indirect observation and use of boron vertex-centered carboranyl radicals generated by the oxidation of modified carboranyl precursors. These radical intermediates are formed by the direct oxidation of a B-B bond between a boron cluster cage and an exopolyhedral boron-based substituent (e.g., -BF3K, -B(OH)(2)). The in situ generated radical species are shown to be competent substrates in reactions with oxygen-based radicals, dichalcogenides, and N-heterocycles, yielding the corresponding substituted carboranes containing B-O, B-S, B-Se, B-Te, and B-C bonds. Remarkably, this chemistry tolerates various electronic environments, providing access to facile substitution chemistry at both electron-rich and electron-poor B-H vertices in carboranes.
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