期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 140, 期 42, 页码 13798-13807出版社
AMER CHEMICAL SOC
DOI: 10.1021/jacs.8b07872
关键词
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资金
- Natural Science Foundation of China [21472166, 21702182]
- National Basic Research Program of China (973 Project) [2015CB856500]
- Chinese 1000 Young Talents Plan
A series of cage penta-arylated carboranes have been synthesized by palladium-catalyzed intermolecular coupling of the C-carboxylic acid of the monocarba-closo-dodecaborate anion [CB11H12](-) with iodoarenes by direct cage B-H bond functionalization. These transformations set a record in terms of one-pot directing group-mediated activation of inert bonds in a single molecule. The methodology is characterized by high yields, good functional group tolerance, and complete cage regioselectivity. The directing group COOH can be easily removed during or after the intermolecular coupling reaction. The mechanistic pathways were probed using density functional theory calculations. A Pd(II)-Pd(IV)-Pd(II) catalytic cycle is proposed, in which initial coupling is followed by preferred B-H activation of the adjacent boron vertex, and continuation of this selectivity results in a continuous walking process of the palladium center. The methodology opens a new avenue toward building blocks with 5-fold symmetry.
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