Palladium-Catalyzed Selective Five-Fold Cascade Arylation of the 12-Vertex Monocarborane Anion by B–H Activation

• Published in: Journal of the American Chemical Society Vol. 140; no. 42; pp. 13798 - 13807
• Main Authors: Lin, Furong, Yu, Jing-Lu, Shen, Yunjun, Zhang, Shuo-Qing, Spingler, Bernhard, Liu, Jiyong, Hong, Xin, Duttwyler, Simon
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 24.10.2018
• Subjects: arylation; boron; carboxylic acids; catalytic activity; chemical bonding; density functional theory; moieties; palladium; regioselectivity; walking
• ISSN: 0002-7863; 1520-5126; 1520-5126
• DOI: 10.1021/jacs.8b07872

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.