Arene C–H borylation strategy enabled by a non-classical boron cluster-based electrophile

Sangmin Kim, Joseph W. Treacy, Yessica A. Nelson, Jordan A. M. Gonzalez, Milan Gembicky, K. N. Houk and Alexander M. Spokoyny ()
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Sangmin Kim: University of California, Los Angeles
Joseph W. Treacy: University of California, Los Angeles
Yessica A. Nelson: University of California, Los Angeles
Jordan A. M. Gonzalez: University of California, Los Angeles
Milan Gembicky: University of California, San Diego
K. N. Houk: University of California, Los Angeles
Alexander M. Spokoyny: University of California, Los Angeles

Nature Communications, 2023, vol. 14, issue 1, 1-9

Abstract: Abstract Introducing a tri-coordinate boron-based functional group (e.g., boronic ester) into an unactivated C–H bond in the absence of directing groups is an ongoing challenge in synthetic chemistry. Despite previous developments in transition metal-catalyzed and -free approaches, C–H borylation of sterically hindered arenes remains a largely unsolved problem to date. Here, we report a synthetic strategy of a two-step, precious metal-free electrophilic C–H borylation of sterically hindered alkyl- and haloarenes to generate aryl boronic esters. The first step relies on electrophilic aromatic substitution (EAS) induced by cage-opening of Cs2[closo-B10H10], forming a 6-Ar-nido-B10H13 product containing a B–C bond, followed by a cage deconstruction of arylated decaboranes promoted by diols. The combination of these two steps allows for the preparation of aryl boronic esters that are hardly accessible by current direct C–H borylation approaches. This reaction does not require any precious metals, highly-engineered ligands, pre-functionalized boron reagents, or inert conditions. In addition, the unique properties of a non-classical boron cluster electrophile intermediate, B10H13+, afford a regioselectivity with unique steric and electronic control without the undesirable side reactions.

Date: 2023
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DOI: 10.1038/s41467-023-37258-6

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