Organophosphorus-catalyzed relay oxidation of H-Bpin: electrophilic C-H borylation of heteroarenes

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Abstract

A nontrigonal phosphorus triamide (1, P{N[o-NMe-C6H4]2}) is shown to catalyze C-H borylation of electron-rich heteroarenes with pinacolborane (HBpin) in the presence of a mild chloroalkane reagent. C-H borylation proceeds for a range of electron-rich heterocycles including pyrroles, indoles, and thiophenes of varied substitution. Mechanistic studies implicate an initial P-N cooperative activation of HBpin by1to giveP-hydrido diazaphospholene2, which is diverted by Atherton-Todd oxidation with chloroalkane to generateP-chloro diazaphospholene3. DFT calculations suggest subsequent oxidation of pinacolborane by3generates chloropinacolborane (ClBpin) as a transient electrophilic borylating species, consistent with observed substituent effects and regiochemical outcomes. These results illustrate the targeted diversion of established reaction pathways in organophosphorus catalysis to enable a new mode of main group-catalyzed C-H borylation.

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Lipshultz, J. M., Fu, Y., Liu, P., & Radosevich, A. T. (2021). Organophosphorus-catalyzed relay oxidation of H-Bpin: electrophilic C-H borylation of heteroarenes. Chemical Science, 12(3), 1031–1037. https://doi.org/10.1039/d0sc05620k

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