Organophosphorus-catalyzed relay oxidation of H-Bpin: electrophilic C–H borylation of heteroarenes
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d0sc05620k.pdf
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Published version
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846.07 KB
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Author(s)
Lipshultz, Jeffrey M
Fu, Yue
Liu, Peng
Radosevich, Alexander T
Date Issued
2021
Journal
Chemical Science
Publisher
Royal Society of Chemistry (RSC)
Citation
Lipshultz, Jeffrey M, Fu, Yue, Liu, Peng and Radosevich, Alexander T. 2021. "Organophosphorus-catalyzed relay oxidation of H-Bpin: electrophilic C–H borylation of heteroarenes." Chemical Science, 12 (3).
Version
Final published version
Abstract
© The Royal Society of Chemistry 2020. 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.
MIT Department
Massachusetts Institute of Technology. Department of Chemistry
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DOI of Published Version
https://doi.org/10.1039/D0SC05620K
