Issue 3, 2023

Regiodivergent metal-catalyzed B(4)- and C(1)-selenylation of o-carboranes


Regiodivergent transition metal-catalyzed B(4)- and C(1)-selenylation reactions of o-carboranes have been demonstrated. Namely, Ru(II)-catalysis selectively generated B(4)-selenylated o-carboranes from the reaction of o-carborane acids with arylselenyl bromides with the release of carbon dioxide. In contrast, Pd(II) catalysis provided exclusively C(1)-selenylated o-carboranes from the decarboxylative reaction of o-carborane acids with diaryl diselenides. In contrast to previous milestones in this area, these reactions demonstrate broad substrate scope with excellent yields. Combination of these methods leads to the formation of B(4)–C(1)-diselenylated o-carboranes. DFT studies revealed the mechanism of the Ru-process, with initial selenylation of the carborane cluster discovered to be essential for an energetically reasonable decarboxylation. This results in selenylation on the B(4) position prior to the decarboxylation event at C(1). This contrasted with the Pd-process in which the ready decarboxylation at C(1) leads to selenylation at C(1).

Graphical abstract: Regiodivergent metal-catalyzed B(4)- and C(1)-selenylation of o-carboranes

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Article information

Article type
Edge Article
08 Oct 2022
01 Dec 2022
First published
03 Dec 2022
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2023,14, 643-649

Regiodivergent metal-catalyzed B(4)- and C(1)-selenylation of o-carboranes

K. Lee, J. L. Harper, T. H. Kim, H. Chan Noh, D. Kim, P. Ha-Yeon Cheong and P. H. Lee, Chem. Sci., 2023, 14, 643 DOI: 10.1039/D2SC05590B

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