Dual Catalysis for the Aerobic Oxidation of Benzyl Alcohols – Nitric Acid and Fluorinated Alcohol. Issue 3 (20th December 2016)

• Record Type: Journal Article
• Authors: Možina, Štefan; Stavber, Stojan; Iskra, Jernej
• Is Part Of: European journal of organic chemistry. Issue 3(2017)
• Page Start: 448
• Page End: 452
• Publication Date: 2016-12-20
• Subjects: Alcohols -- Nitric acid -- Oxidation -- Perfluorinated solvents -- Template catalysis; Chemistry, Organic -- Periodicals; Organic compounds -- Synthesis -- Periodicals; Bioorganic chemistry -- Periodicals; Chemistry, Physical organic -- Periodicals; 547
• DOI: 10.1002/ejoc.201601339
• Languages: English
• ISSNs: 1434-193X

Abstract

Abstract : Benzyl alcohols were oxidized with oxygen to aldehydes in excellent yields with high selectivities at room temperature. Dual catalysis was operative with HNO3 as the oxidant and precursor of the nitrogen oxides and with the use of 1, 1, 1, 3, 3, 3‐hexafluoro‐2‐propanol as a template catalyst and solvent. Fluorinated alcohols also increased the selectivity by inhibiting further oxidation to benzoic acids. Activation of nitric acid catalyzed aerobic oxidation by the fluorinated solvent made the use of 2, 2, 6, 6‐tetramethylpiperidin‐1‐oxyl (TEMPO) or a metal catalyst superfluous. Abstract : Benzyl alcohols are oxidized with oxygen to aldehydes in excellent yields with high selectivities at room temperature with HNO3 as the catalyst and 1, 1, 1, 3, 3, 3‐hexafluoro‐2‐propanol (HFIP) as a template catalyst. The latter also inhibits further oxidation to benzoic acids.