A Facile Strategy to a New Fluorous-Tagged, Immobilized TEMPO Catalyst Using a Click Reaction, and Its Catalytic Activity

Alexandru Gheorghe; Erick Cuevas-Yañez; Joachim Horn; Willi Bannwarth; Banda Narsaiah; Oliver Reiser

doi:10.1055/s-2006-950256

LETTER

A Facile Strategy to a New Fluorous-Tagged, Immobilized TEMPO Catalyst Using a Click Reaction, and Its Catalytic Activity

Alexandru Gheorghe^a, Erick Cuevas-Yañez^a, Joachim Horn^b, Willi Bannwarth^b, Banda Narsaiah*^c, Oliver Reiser*^a
^a Institut für Organische Chemie der Universität Regensburg, Universitätsstr. 31, 93053 Regensburg, Germany
Fax: +49(941)9434121; e-Mail: Oliver.Reiser@chemie.uni-regensburg.de;
^b Institut für Organische Chemie und Biochemie, Albert-Ludwigs-Universität Freiburg, Albertstr. 21, 79104 Freiburg, Germany
^c Indian Institute of Chemical Technology, Division of Fluoro Organics, Uppal Road, Hyderabad 500007, AP, India

Abstract

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Abstract

A new fluorous-tagged TEMPO catalyst was prepared by a facile approach using the copper-catalyzed azide-alkyne cycloaddition as the ligation method. A fluorous F₁₇-CLICK-TEMPO showed excellent activity and selectivity in the oxidation of alcohols to aldehydes using bleach as the terminal oxidant. Moreover, the catalyst could be easily recovered using silica gel 60 and recycled in four cycles without loss of activity.

Key words

catalyst immobilization - fluorous - oxidation - click chemistry - TEMPO

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References

References and Notes

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Propargyl Ether TEMPO 2: To a stirring suspension of NaH (60% in mineral oil, 830 mg, 20.75 mmol) in dry DMF (10 mL), 4-hydroxy TEMPO (1, 3.0 g, 17.44 mmol) was added portionwise at 0 °C and stirred at r.t. for 50 min. Propargyl bromide (1.85 mL, 21.0 mmol) was added dropwise at 0 °C over a period of 45 min. The resulting mixture was stirred at r.t. overnight. The reaction mixture was poured into ice water (80 mL) and was extracted with EtOAc (4 × 25 mL). The combined organics were washed with brine (2 × 30 mL), dried over MgSO₄, filtered and evaporated under reduced pressure. The residue was purified by column chromatography (silica gel, hexanes-EtOAc, 9:1) to give the title compound 2 (2.85 g, 78%) as an orange solid. ¹H NMR and ¹³C NMR spectra were identical to those previously reported. [10]

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F ₁₇ -CLICK-TEMPO 6: To a stirred mixture of 1-azido-perfluorodecane (4, 1.19 g, 2.43 mmol) and propargyl ether TEMPO 2 (0.95 g, 4.54 mmol) in degassed THF (15 mL), CuI (27 mg, 6 mol%) was added. The resulting mixture was stirred under a nitrogen atmosphere at r.t. for 1 day. Then, the solvent was removed in vacuo and the residue was purified by column chromatography (silica gel, hexanes-EtOAc, 5:1 → 1:1) to give some of the recovered TEMPO 2 (0.4 g, 42%) and the title compound 6 (1.35 g, 80% based on 4, 73% based on consumed 2) as a light orange solid. Mp 105-107 °C; IR (KBr): 2984, 1468, 1371, 1410, 1177, 1142, 1084, 1045, 989, 957, 661 cm^-1; MS (PI-EI, 70 eV): m/z 699 [M⁺]; HRMS: m/z [M + H⁺] calcd for C₂₂H₂₄F₁₇N₄O₂: 699.1628; found: 699.1620.

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General Procedure for the Oxidation of Alcohols by F ₁₇ -CLICK-TEMPO 6/Bleach: Alcohol (1.0 mmol) in 2 mL CH₂Cl₂, KBr (24 mg, 0.2 mmol) in H₂O (2 mL) and
F₁₇-CLICK-TEMPO 6 (7 mg, 1 mol%) were added to a round-bottom flask. The reaction mixture was stirred at 0 °C before addition of NaOCl (0.8 mL, 10%) and NaHCO₃ (40 mg, 50 mg·mL^-1, bleach). The resulting mixture was stirred at 0 °C for 15 min. The reaction was quenched by the addition of H₂O (5 mL) and the organic layer was extracted with CH₂Cl₂ (2 × 5 mL). The combined organic layers were dried over anhydrous Na₂SO₄ and concentrated in vacuo to give crude product, which was placed on a short bed of silica and eluted with CH₂Cl₂ in order to obtain pure aldehyde.

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Aerobic Oxidation of 4-Bromobenzyl Alcohol by F ₁₇ -CLICK-TEMPO 6; Recycling Experiments: 4-Bromo-benzyl alcohol (2.0 g, 10.7 mmol) in CH₂Cl₂ (20 mL), KBr (257 mg, 2.16 mmol) in H₂O (2 mL) and F₁₇-CLICK-TEMPO 6 (75 mg, 1 mol%) were added to a round-bottom flask. The reaction mixture was stirred at 0 °C before addition of NaOCl (8.6 mL, 14 mmol), NaHCO₃ (430 mg, 50 mg·mL^-1, bleach), stirring then continued at 0 °C for 15 min. The reaction was quenched by addition of H₂O (10 mL) and the organic layer was extracted with CH₂Cl₂ (2 × 10 mL). The combined organic layers were dried over anhydrous Na₂SO₄ and concentrated to give crude product, which was placed on a short bed of silica (5 g) and eluted with CH₂Cl₂ in order to obtain 4-bromobenzylaldehyde. The catalyst was recovered from the column by elution with Et₂O and used in the next cycle.