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Hypervalent iodine oxides and chloride for the conversion of light alkanes to mono-functionalized products: A radical-based process for selective partial oxidation

Schwartz, Nichole and Boaz, Nicholas and Fortman, George and Kalman, Steven and Goldberg, Jonathan and Fu, Ross and Nielsen, Robert and Goddard, William and Groves, John and Gunnoe, Thomas (2018) Hypervalent iodine oxides and chloride for the conversion of light alkanes to mono-functionalized products: A radical-based process for selective partial oxidation. In: 256th American Chemical Society National Meeting & Exposition, 19-23 August 2018, Boston, MA. https://resolver.caltech.edu/CaltechAUTHORS:20181108-144800620

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Abstract

A process for the partial oxidn. of light alkanes to mono-functionalized products in high conversion and yield has been highly sought after. With mixts. of iodine oxide and chloride salts in trifluoroacetic acid solvent, light alkanes are converted to alkyl esters in good yields (40-50%) and selectivity. The reactions can be driven thermally or photolytically. While the process exhibits similarities to radical chlorination and oxychlorination chem., the obsd. selectivity for the mono-functionalized product is unique to the iodine oxide and chloride process. The elucidation of the reaction mechanism has involved studies with adamantane as a model to examine the selectivity and kinetic isotope effect of the reaction vs. radical chlorination. The extent of the protecting effect of the ester group of the product has been investigated for MeX and EtX species. The exptl. study, supported by calcns., indicates that a radical-based reaction pathway which is catalytic in chloride results in the formation of alkyl esters that are protected from over-oxidn. These findings have enabled the extension of this system to alternative oxidants.


Item Type:Conference or Workshop Item (Paper)
Related URLs:
URLURL TypeDescription
https://global.acs.org/events/256th-acs-national-meeting-expositionOrganizationConference Website
ORCID:
AuthorORCID
Nielsen, Robert0000-0002-7962-0186
Goddard, William0000-0003-0097-5716
Groves, John0000-0002-9944-5899
Additional Information:© 2018 American Chemical Society.
Record Number:CaltechAUTHORS:20181108-144800620
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20181108-144800620
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:90769
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:13 Nov 2018 18:12
Last Modified:03 Oct 2019 20:28

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