Mechanism of Hydrocarbon Functionalization by an Iodate/Chloride System: The Role of Ester Protection
Abstract
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.
- Authors:
-
[2];
[2];
[3];
[1]
- 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
- Publication Date:
- Research Org.:
- Univ. of Virginia, Charlottesville, VA (United States)
- Sponsoring Org.:
- USDOE Office of Energy Efficiency and Renewable Energy (EERE)
- OSTI Identifier:
- 1596591
- Grant/Contract Number:
- AC07-05ID14517
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 8; Journal Issue: 4; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
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., and Gunnoe, T. Brent. Mechanism of Hydrocarbon Functionalization by an Iodate/Chloride System: The Role of Ester Protection. United States: N. p., 2018.
Web. doi:10.1021/acscatal.7b04397.
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. Mechanism of Hydrocarbon Functionalization by an Iodate/Chloride System: The Role of Ester Protection. United States. https://doi.org/10.1021/acscatal.7b04397
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., and Gunnoe, T. Brent. Thu .
"Mechanism of Hydrocarbon Functionalization by an Iodate/Chloride System: The Role of Ester Protection". United States. https://doi.org/10.1021/acscatal.7b04397. https://www.osti.gov/servlets/purl/1596591.
@article{osti_1596591,
title = {Mechanism of Hydrocarbon Functionalization by an Iodate/Chloride System: The Role of Ester Protection},
author = {Schwartz, Nichole A. and Boaz, Nicholas C. and Kalman, Steven E. and Zhuang, Thompson and Goldberg, Jonathan M. and Fu, Ross and Nielsen, Robert J. and Goddard, William A. and Groves, John T. and Gunnoe, T. Brent},
abstractNote = {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.},
doi = {10.1021/acscatal.7b04397},
journal = {ACS Catalysis},
number = 4,
volume = 8,
place = {United States},
year = {Thu Mar 01 00:00:00 EST 2018},
month = {Thu Mar 01 00:00:00 EST 2018}
}
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