Aluminium‐Catalyzed C(sp)−H Borylation of Alkynes

Dominic R Willcox, Daniel M De Rosa, Jack Howley, Abigail Levy, Alan Steven, Gary S Nichol, Carole A Morrison, Michael J Cowley, Stephen P Thomas

Research output: Contribution to journalArticlepeer-review

Abstract / Description of output

Historically used in stoichiometric hydroalumination chemistry, recent advances have transformed aluminium hydrides into versatile catalysts for the hydroboration of unsaturated multiple bonds. This catalytic ability is founded on the defining reactivity of aluminium hydrides with alkynes and alkenes: 1,2-hydroalumination of the unsaturated π-system. This manuscript reports the aluminium-hydride catalyzed dehydroborylation of terminal alkynes. A tethered intramolecular amine ligand controls reactivity at the aluminium hydride centre, switching off hydroalumination and instead enabling selective reactions at the alkyne C–H σ-bond. Chemoselective C‒H borylation was observed across a series of aryl- and alkyl substituted alkynes (21 examples). On the basis of kinetic and density functional theory studies, a mechanism in which C–H borylation proceeds by σ-bond metathesis between pinacolborane (HBpin) and alkynyl aluminium intermediates is proposed.
Original languageEnglish
JournalAngewandte Chemie International Edition
Early online date9 Jun 2021
Publication statusE-pub ahead of print - 9 Jun 2021


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