Accelerating Effect of the Addition of HFIP on the Oxidation of Alcohols Using TEMPO/PIDA

Abstract

The accelerating effect of the addition of 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) on the oxidation of alcohols using 2,2,6,6-tetramethylpiperidine-N-oxyl (TEMPO) in combination with phenyliodine(III) diacetate (PIDA) was investigated. HFIP accelerates the oxidation of primary and secondary alcohols that are not sterically hindered. Based on the results in this study, the acceleration effect of HFIP may be due to the acceleration of the re-oxidation step by PIDA.

Key words

TEMPO - nitroxyl radical - HFIP - PIDA - hypervalent iodine - oxidation

Publikationsverlauf

Eingereicht: 04. April 2025

Angenommen nach Revision: 25. April 2025

Artikel online veröffentlicht:
04. Juni 2025

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• 15 3-Phenylpropanal (2b); Typical Procedure To a mixture of 1b (136 mg, 1.00 mmol), TEMPO (15.6 mg, 100 μmol), and HFIP (105 μL, 1.00 mmol) in DCM (10 mL) was added PIDA (483 mg, 1.50 mmol), and the mixture was stirred at r.t. for 1.5 h. The reaction was quenched with sat. aq. NaHCO₃ and extracted with CH₂Cl₂. The organic layer was dried (Na₂SO₄), filtered, and concentrated in vacuo to give a residue. The residue was purified by MPLC (n-hexane/AcOEt = 1:0 to 4:1) to give 2b (117 mg, 87%) as a colorless oil.^{16 1}H NMR (400 MHz, CDCl₃): δ = 9.84–9.81 (m, 1H), 7.34–7.27 (m, 2H), 7.25–7.17 (m, 3H), 2.98 (t, J = 7.2 Hz, 2H), 2.80 (t, J = 7.5 Hz, 2H). ¹³C NMR (101 MHz, CDCl₃): δ = 201.7, 140.4, 128.7, 128.4, 126.4, 45.3, 28.2.
• 16 NMR spectra of the obtained product were consistent with the reported one: Erbing E, Vázquez-Romero A, Bermejo Gómez A, Platero-Prats AE, Carson F, Zou X, Tolstoy P, Martín-Matute B. Chem. Eur. J. 2016; 22: 15659