Aerobic Oxidation of Secondary Alcohols with Nitric Acid and Iron(III) Chloride as Catalysts in Fluorinated Alcohol

Autor:	Štefan Možina, Jernej Iskra
Rok vydání:	2019
Předmět:	chemistry.chemical_classification chemistry.chemical_compound Ketone chemistry Nitric acid Organic Chemistry Oxidation of secondary alcohols to ketones Alcohol Primary alcohol Medicinal chemistry Chemical reaction Iron(III) chloride Catalysis
Zdroj:	The Journal of Organic Chemistry. 84:14579-14586
ISSN:	1520-6904 0022-3263
DOI:	10.1021/acs.joc.9b02109
Popis:	Fluorinated alcohols as solvents strongly influence and direct chemical reaction through donation of strong hydrogen bonds while being weak acceptors. We used 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) as the activating solvent for a nitric acid and FeCl3-catalyzed aerobic oxidation of secondary alcohols to ketones. Reaction proceeded selectively with excellent yields with no reaction on the primary alcohol group. Oxidation of benzyl alcohols proceeds selectively to aldehydes with only HNO3 as the catalyst, while reaction on tertiary alcohols proceeds through dehydration and dimerization. A mechanistic study showed in situ formation of NOCl that converts alcohol into alkyl nitrite, which in the presence of Fe3+ ions and fluorinated alcohol decomposes into ketone. The study indicates that iron(III) acts also as the single-electron transfer catalyst in regeneration of NOCl reactive species.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::1d51f3e4f0104d857ffa307f14246189 https://doi.org/10.1021/acs.joc.9b02109 Zobrazit plný text záznamu