Microwave-assisted C–H oxidation of methylpyridylheteroarenes via a Kornblum-Type reaction
Abstract
Expansion of the operational capacity of soft-Lewis basic complexant scaffolds towards improved physical properties for the chemoselective sequestration of minor actinides from the electronically similar lanthanides necessitates rapid access to synthons for efficient complexant construction for downstream employment in separations assays. Pursuant to the aforementioned, we were interested in exploring the potential utility of advanced, unsymmetric heteroarene constructs for separations which required access to pyridyl carbaldehydes. Limited commercial availability of synthetic precursors inspired our effort to define a chemoselective, microwave assisted, Kornblum-type reaction via C–H functionalization. This efficient reaction sequence uses I2 as a mild oxidant without acidic or basic additives, in concert with DMSO as the solvent and putative oxygen source to afford a diverse array of heteroaryl products devoid of competitive remote methyl group oxidation, or degradation of the heteroaryl N atom. Finally, method development, substrate scope, and a preliminary mechanistic hypothesis supported by Density Functional Theory are presented herein.
- Authors:
-
- Tennessee Technological Univ., Cookeville, TN (United States)
- Univ. of Alabama, Tuscaloosa, AL (United States)
- Publication Date:
- Research Org.:
- Tennessee Technological Univ., Cookeville, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
- OSTI Identifier:
- 1977688
- Alternate Identifier(s):
- OSTI ID: 1870338
- Grant/Contract Number:
- SC0018033
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Tetrahedron
- Additional Journal Information:
- Journal Volume: 116; Journal Issue: C; Journal ID: ISSN 0040-4020
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; C-H oxidation; Kornblum oxidation; heteroarene; Pyridine; 1,2,4-triazine
Citation Formats
Tedder, Mariah L., Dzeagu, Fortune O., Mason, Marcos M., Dixon, David A., and Carrick, Jesse D. Microwave-assisted C–H oxidation of methylpyridylheteroarenes via a Kornblum-Type reaction. United States: N. p., 2022.
Web. doi:10.1016/j.tet.2022.132805.
Tedder, Mariah L., Dzeagu, Fortune O., Mason, Marcos M., Dixon, David A., & Carrick, Jesse D. Microwave-assisted C–H oxidation of methylpyridylheteroarenes via a Kornblum-Type reaction. United States. https://doi.org/10.1016/j.tet.2022.132805
Tedder, Mariah L., Dzeagu, Fortune O., Mason, Marcos M., Dixon, David A., and Carrick, Jesse D. Wed .
"Microwave-assisted C–H oxidation of methylpyridylheteroarenes via a Kornblum-Type reaction". United States. https://doi.org/10.1016/j.tet.2022.132805. https://www.osti.gov/servlets/purl/1977688.
@article{osti_1977688,
title = {Microwave-assisted C–H oxidation of methylpyridylheteroarenes via a Kornblum-Type reaction},
author = {Tedder, Mariah L. and Dzeagu, Fortune O. and Mason, Marcos M. and Dixon, David A. and Carrick, Jesse D.},
abstractNote = {Expansion of the operational capacity of soft-Lewis basic complexant scaffolds towards improved physical properties for the chemoselective sequestration of minor actinides from the electronically similar lanthanides necessitates rapid access to synthons for efficient complexant construction for downstream employment in separations assays. Pursuant to the aforementioned, we were interested in exploring the potential utility of advanced, unsymmetric heteroarene constructs for separations which required access to pyridyl carbaldehydes. Limited commercial availability of synthetic precursors inspired our effort to define a chemoselective, microwave assisted, Kornblum-type reaction via C–H functionalization. This efficient reaction sequence uses I2 as a mild oxidant without acidic or basic additives, in concert with DMSO as the solvent and putative oxygen source to afford a diverse array of heteroaryl products devoid of competitive remote methyl group oxidation, or degradation of the heteroaryl N atom. Finally, method development, substrate scope, and a preliminary mechanistic hypothesis supported by Density Functional Theory are presented herein.},
doi = {10.1016/j.tet.2022.132805},
journal = {Tetrahedron},
number = C,
volume = 116,
place = {United States},
year = {Wed May 11 00:00:00 EDT 2022},
month = {Wed May 11 00:00:00 EDT 2022}
}
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