Remote, Late-Stage Oxidation of Aliphatic C-H Bonds in Amide-Containing Molecules
| Autor: | Takeshi Nanjo, M. Christina White, Emílio C. de Lucca |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
Pyridones
Salt (chemistry) Electrons 010402 general chemistry 01 natural sciences Biochemistry Catalysis Article chemistry.chemical_compound Colloid and Surface Chemistry Amide Organic chemistry Molecule Anilides Methyl trifluoromethanesulfonate chemistry.chemical_classification Biological Products Primary (chemistry) 010405 organic chemistry Late stage General Chemistry Amides Carbon 0104 chemical sciences chemistry Pharmaceutical Preparations Carbamates Peptides Oxidation-Reduction Hydrogen |
| Zdroj: | Journal of the American Chemical Society. 139(41) |
| ISSN: | 1520-5126 |
| Popis: | Amide-containing molecules are ubiquitous in natural products, pharmaceuticals, and materials science. Due to their intermediate electron-richness, they are not amenable to any of the previously developed N-protection strategies known to enable remote aliphatic C—H oxidations. Using information gleaned from a systematic study of the main features that makes remote oxidations of amides in peptide settings possible, we developed an imidate salt protecting strategy that employs methyl trifluoromethanesulfonate (MeOTf) as a reversible alkylating agent. The imidate salt strategy enables, for the first time, remote, non-directed, site-selective C(sp3)—H oxidation with Fe(PDP) and Fe(CF3PDP) catalysis in the presence of a broad scope of tertiary amides, anilide, 2-pyridone, and carbamate functionality. Secondary and primary amides can be masked as N-Ns amides to undergo remote oxidation. This novel imidate strategy facilitates late-stage oxidations in a broader scope of medicinally important molecules and may find use in other C—H oxidations and metal-mediated reactions that do not tolerate amide functionality. |
| Databáze: | OpenAIRE |
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