Mechanism of Hydrocarbon Functionalization by an Iodate/Chloride System: The Role of Ester Protection

Schwartz, Nichole A.; Boaz, Nicholas C.; Kalman, Steven E.; Zhuang, Thompson; Goldberg, Jonathan M.; Fu, Ross; Nielsen, Robert J.; Goddard, William A.; Groves, John T.; Gunnoe, T. Brent

doi:10.1021/acscatal.7b04397

Mechanism of Hydrocarbon Functionalization by an Iodate/Chloride System: The Role of Ester Protection

Journal Article · Thu Mar 01 00:00:00 EST 2018 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.7b04397· OSTI ID:1596591

Schwartz, Nichole A. ^[1]; Boaz, Nicholas C. ^[2]; Kalman, Steven E. ^[2]; Zhuang, Thompson ^[2]; Goldberg, Jonathan M. ^[2]; Fu, Ross ^[3]; ^[3]; ^[3]; ^[4]; ^[2]

Univ. of Virginia, Charlottesville, VA (United States). Dept. of Chemistry; University of Virginia
Univ. of Virginia, Charlottesville, VA (United States). Dept. of Chemistry
California Inst. of Technology (CalTech), Pasadena, CA (United States). Materials and Process Simulation Center
Princeton Univ., NJ (United States). Dept. of Chemistry

Mixtures of chloride and iodate salts for light alkane oxidation achieve > 20% yield of methyl trifluoroacetate (TFA) from methane with > 85% selectivity (J. Am. Chem. Soc. 2014, 136, 8393-8401). The mechanism of this C–H oxygenation has been probed by examining adamantane as a model substrate. These recent results lend support to the involvement of free radicals. Comparative studies between radical chlorination and iodate/chloride functionalization of adamantane afford statistically identical 3°:2° selectivities (~5.2:1) and kinetic isotope effects for C–H/C–D functionalization {kH/kD = 1.52(3) and 1.6(3)}. Alkane functionalization by iodate/chloride in HTFA is proposed to occur through H-atom abstraction by free radical species including Cl· to give alkyl radicals. Iodine, which forms by in situ reduction of iodate, traps the alkyl radicals as alkyl radicals that are subsequently converted to alkyl esters in HTFA solvent. Importantly, the alkyl ester products (RTFA) are quite stable to further oxidation under the oxidizing conditions due to the protecting nature of the ester moiety.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Virginia, Charlottesville, VA (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

Grant/Contract Number:: AC07-05ID14517

OSTI ID:: 1596591

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 4 Vol. 8; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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