Cp* iridium precatalysts for selective C–H oxidation with sodium periodate as the terminal oxidant

Meng Zhou, Ulrich Hintermair, Brian G. Hashiguchi, Alexander R. Parent, Sara M. Hashmi, Menachem Elimelech, Roy A. Periana, Gary W. Brudvig, Robert H. Crabtree

Research output: Contribution to journalArticle

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Abstract

Sodium periodate (NaIO4) is shown to be a milder and more efficient terminal oxidant for C–H oxidation with Cp*Ir (Cp* = C5Me5) precatalysts than ceric(IV) ammonium nitrate. Synthetically useful yields, regioselectivities, and functional group tolerance were found for methylene oxidation of substrates bearing a phenyl, ketone, ester, or sulfonate group. Oxidation of the natural products (−)-ambroxide and sclareolide proceeded selectively, and retention of configuration was seen in cis-decalin hydroxylation. At 60 °C, even primary C–H bonds can be activated: whereas methane was overoxidized to CO2 in 39% yield without giving partially oxidized products, ethane was transformed into acetic acid in 25% yield based on total NaIO4. 18O labeling was demonstrated in cis-decalin hydroxylation with 18OH2 and NaIO4. A kinetic isotope effect of 3.0 ± 0.1 was found in cyclohexane oxidation at 23 °C, suggesting C–H bond cleavage as the rate-limiting step. Competition experiments between C–H and water oxidation show that C–H oxidation of sodium 4-ethylbenzene sulfonate is favored by 4 orders of magnitude. In operando time-resolved dynamic light scattering and kinetic analysis exclude the involvement of metal oxide nanoparticles and support our previously suggested homogeneous pathway.
Original languageEnglish
Pages (from-to)957-965
Number of pages9
JournalOrganometallics
Volume32
Issue number4
Early online date6 Feb 2013
DOIs
Publication statusPublished - 25 Feb 2013

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Iridium
iridium
Oxidants
sodium
Oxidation
oxidation
Hydroxylation
sulfonates
Bearings (structural)
ammonium nitrates
Regioselectivity
Kinetics
Ethane
Methane
kinetics
Dynamic light scattering
products
Biological Products
Ketones
acetic acid

Cite this

Zhou, M., Hintermair, U., Hashiguchi, B. G., Parent, A. R., Hashmi, S. M., Elimelech, M., ... Crabtree, R. H. (2013). Cp* iridium precatalysts for selective C–H oxidation with sodium periodate as the terminal oxidant. Organometallics, 32(4), 957-965. https://doi.org/10.1021/om301252w

Cp* iridium precatalysts for selective C–H oxidation with sodium periodate as the terminal oxidant. / Zhou, Meng; Hintermair, Ulrich; Hashiguchi, Brian G.; Parent, Alexander R.; Hashmi, Sara M.; Elimelech, Menachem; Periana, Roy A.; Brudvig, Gary W.; Crabtree, Robert H.

In: Organometallics, Vol. 32, No. 4, 25.02.2013, p. 957-965.

Research output: Contribution to journalArticle

Zhou, M, Hintermair, U, Hashiguchi, BG, Parent, AR, Hashmi, SM, Elimelech, M, Periana, RA, Brudvig, GW & Crabtree, RH 2013, 'Cp* iridium precatalysts for selective C–H oxidation with sodium periodate as the terminal oxidant', Organometallics, vol. 32, no. 4, pp. 957-965. https://doi.org/10.1021/om301252w
Zhou, Meng ; Hintermair, Ulrich ; Hashiguchi, Brian G. ; Parent, Alexander R. ; Hashmi, Sara M. ; Elimelech, Menachem ; Periana, Roy A. ; Brudvig, Gary W. ; Crabtree, Robert H. / Cp* iridium precatalysts for selective C–H oxidation with sodium periodate as the terminal oxidant. In: Organometallics. 2013 ; Vol. 32, No. 4. pp. 957-965.
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