Aerobic Oxidation of Secondary Alcohols with Nitric Acid and Iron(III) Chloride as Catalysts in Fluorinated Alcohol
作者:Štefan Možina、Jernej Iskra
DOI:10.1021/acs.joc.9b02109
日期:2019.11.15
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
氟化醇作为溶剂通过提供强氢键而又是弱受体而强烈影响并指导化学反应。我们使用1,1,1,3,3,3-六氟-2-丙醇(HFIP)作为硝酸的活化溶剂,并将FeCl3催化的仲醇有氧氧化成酮。反应以优异的收率选择性地进行,而在伯醇基上没有反应。仅以HNO3为催化剂,苄醇的氧化选择性地发展为醛,而叔醇的反应则通过脱水和二聚进行。机理研究表明,NOCl的原位形成将乙醇转化为亚硝酸烷基酯,而在存在Fe3 +离子和氟化醇的情况下,NOCl分解为酮。