Mechanistic Studies of Cobalt-Catalyzed C(sp2 )-H Borylation of Five-Membered Heteroarenes with Pinacolborane

ACS Catalysis
Jennifer V Obligacion, Paul J Chirik

Abstract

Studies into the mechanism of cobalt-catalyzed C(sp2)-H borylation of five-membered heteroarenes with pinacolborane (HBPin) as the boron source established the catalyst resting state as the trans-cobalt(III) dihydride boryl, (iPrPNP)Co(H)2(BPin) (iPrPNP = 2,6-(iPr2PCH2)2(C5H3N)), at both low and high substrate conversions. The overall first-order rate law and observation of a normal deuterium kinetic isotope effect on the borylation of benzofuran versus benzofuran-2-d1 support H2 reductive elimination from the cobalt(III) dihydride boryl as the turnover-limiting step. These findings stand in contrast to that established previously for the borylation of 2,6-lutidine with the same cobalt precatalyst, where borylation of the 4-position of the pincer occurred faster than the substrate turnover and arene C-H activation by a cobalt(I) boryl is turnover-limiting. Evaluation of the catalytic activity of different cobalt precursors in the C-H borylation of benzofuran with HBPin established that the ligand design principles for C- H borylation depend on the identities of both the arene and the boron reagent used: electron-donating groups improve catalytic activity of the borylation of pyridines and arenes with B2Pin2, whereas electron-wi...Continue Reading

References

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Mar 5, 2014·Journal of the American Chemical Society·Jennifer V ObligacionPaul J Chirik
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Mar 18, 2015·Chemical Communications : Chem Comm·Takayuki FurukawaNaoto Chatani
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Aug 2, 2016·Journal of the American Chemical Society·Jennifer V ObligacionPaul J Chirik

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Citations

Feb 20, 2018·Israel Journal of Chemistry·Jennifer V ObligacionPaul J Chirik
Jul 31, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Wiebke DammannPeter Burger
Sep 6, 2018·Chemistry : a European Journal·Kathrin JungeMatthias Beller
Mar 4, 2021·ACS Central Science·Toryn DaltonFrank Glorius
May 16, 2019·Journal of the American Chemical Society·Rebeca Arevalo, Paul J Chirik
Sep 5, 2019·Organometallics·Stephan M RummeltPaul J Chirik
Oct 8, 2021·Chemical Reviews·Shubhankar Kumar BoseTodd B Marder
Dec 31, 2021·Chemical Reviews·Bogdan MarciniecHieronim Maciejewski

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