TEMPO-Mediated Oxidation of Alcohols with Ion-Supported (Diacetoxyiodo)benzenes

Abstract

The oxidation of secondary alcohols and primary alcohols with novel ion-supported (diacetoxyiodo)benzenes (IS-DIB) in the presence of a catalytic amount of 2,2,6,6-tetramethylpiperidine-1-oxy radical (TEMPO) in dichloromethane at room temperature proceeded efficiently to provide the corresponding ketones and aldehydes, respectively, in good yields with high purity. Isolation of the product was easily accomplished by simple diethyl ether extraction of the reaction mixture and subsequent removal of the solvent from the extract. Moreover, ion-supported iodobenzenes, which were co-products derived from IS-DIB in the present oxidation, were recovered in good yields and could be re-oxidized to IS-DIB for reuse in the same oxidation.

Key words

oxidation - ion-supported (diacetoxyiodo)benzene - alcohol - TEMPO - aldehyde - ketone - reuse

• References

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• 8 Typical Procedure for the Preparation of N-Methyl-N-[3-(4′-iodophenyl)-1-propyl]pyrrolidinium 4′′-Methyl-benzenesulfonate (pre-A): To a solution of 3-(4′-iodophenyl)-1-propyl tosylate (5 mmol, 2.08 g) in MeCN (20 mL) was added 1-methylpyrrolidine (1.10 equiv, 5.50 mmol, 0.585 mL). The mixture was stirred for 16 h at 60 °C. After the reaction, the reaction mixture was concentrated in vacuo. H₂O (20 mL) was added to the residue, the aqueous layer was washed with Et₂O (30 mL) once and then extracted with CHCl₃ (3 × 30 mL). The organic layer was dried over Na₂SO₄. Then, removal of the solvent under reduced pressure afforded N-methyl-N-[3-(4′-iodophenyl)-1-propyl]pyrrolidinium 4′′-methylbenzenesulfonate (pre-A) in 99% yield. If necessary, the residue was washed with EtOAc to afford the product in >99% purity. N-Methyl-N-[3-(4′-iodophenoxy)-1-propyl]pyrrolidinium 4′′-methylbenzene-sulfonate (pre-B) and N-[3-(4′-iodophenoxy)-1-propyl]-N,N,N-trimethylammonium 4′′-methylbenzenesulfonate (pre-C) were prepared in 99% yield and 99% yield, respectively, by the same procedure. N-Methyl-N-[3-(4′-iodophenyl)-1-propyl]pyrrolidinium 4′′-Methylbenzenesulfonate: mp 127–129 °C. IR (Nujol): 1185, 798 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 1.93–2.03 (m, 2 H), 2.05–2.10 (m, 4 H), 2.31 (s, 3 H), 2.57 (t, J = 7.5 Hz, 2 H), 3.09 (s, 3 H), 3.50 (t, J = 6.7 Hz, 2 H), 3.53–3.65 (m, 4 H), 6.90 (d, J = 8.2 Hz, 2 H), 7.11 (d, J = 8.2 Hz, 2 H), 7.54 (d, J = 8.2 Hz, 2 H), 7.73 (d, J = 8.2 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 21.27, 21.54, 25.44, 31.57, 48.26, 63.20, 64.20, 91.63, 125.79, 128.67, 130.53, 137.65, 139.25, 139.48, 144.02. ESI-HMRS: m/z calcd for C₁₄H₂₁NI [M⁺]: 330.0713; found: 330.0705. N-Methyl-N-[3-(4′-iodophenoxy)-1-propyl]pyrroli-dinium 4′′-Methylbenzenesulfonate: mp 114–116 °C. IR (Nujol): 1195, 1010, 818 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 2.08–2.23 (m, 6 H), 2.30 (s, 3 H), 3.15 (s, 3 H), 3.54–3.72 (m, 6 H), 3.92 (t, J = 5.8 Hz, 2 H), 6.60 (d, J = 9.1 Hz, 2 H), 7.09 (d, J = 8.2 Hz, 2 H), 7.50 (d, J = 9.1 Hz, 2 H), 7.71 (d, J = 8.2 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 21.23, 21.55, 23.99, 48.27, 61.16, 64.27, 64.38, 83.24, 116.90, 125.70, 128.63, 138.22, 139.22, 144.02, 158.04. ESI-HMRS: m/z calcd for C₁₄H₂₁ONI [M⁺]: 346.0662; found: 346.0655. N-[3-(4′-Iodophenoxy)-1-propyl]-N,N,N-trimethyl-ammonium 4′′-Methylbenzenesulfonate: mp 222–226 °C. IR (KBr) 1285, 1010, 816 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 2.12–2.19 (m, 2 H), 2.29 (s, 3 H), 3.08 (s, 9 H), 3.46 (t, J = 8.3 Hz, 2 H), 4.02 (t, J = 6.0 Hz, 2 H), 6.80 (d, J = 9.0 Hz, 2 H), 7.12 (d, J = 7.9 Hz, 2 H), 7.47 (d, J = 7.9 Hz, 2 H), 7.61 (d, J = 9.0 Hz, 2 H). ¹³C NMR (100 MHz, DMSO): δ = 20.74, 22.42, 52.25, 62.84, 64.84, 83.53, 117.29, 125.44, 128.00, 137.51, 138.01, 145.80, 158.04. HRMS (APPI): m/z calcd for C₁₂H₁₉ONI [M⁺]: 320.0506; found: 320.0499. Typical Procedure for the Preparation of N-Methyl-N-[3-(4′-diacetoxyiodo)phenyl-1-propyl]pyrrolidinium 4′′-Methylbenzenesulfonate (IS-DIB A): To a solution of N-methyl-N-[3-(4′-iodophenyl)-1-propyl]pyrrolidium 4′′-methylbenzenesulfonate (5 mmol, 2.50 g) in AcOH (50 mL) was added portionwise NaBO₃·4H₂O (10 equiv, 50 mmol, 7.69 g). The mixture was stirred for 15 h at 45 °C. After the reaction, the reaction mixture was concentrated in vacuo, then the residue was dissolved in H₂O (50 mL), and the obtained mixture was washed with Et₂O (50 mL) once. Then, the aqueous layer was extracted with CHCl₃ (5 × 30 mL). The organic layer was dried over Na₂SO₄. Removal of the solvent under reduced pressure afforded N-methyl-N-[3-(4′-diacetoxyiodo)-phenyl-1-propyl]pyrrolidium 4′′-methylbenzenesulfonate in the range of 60–70% yields (counteranion; TsO^–/AcO^– = 1:1; IS-DIB A). The counteranion was completely converted into the tosylate anion by the stirring treatment of the obtained IS-DIB A with PTSA·H₂O (1.0 equiv) in MeCN (20 mL) at r.t. overnight. Then the solvent was removed, and H₂O (20 mL) was added to the residue. The aqueous layer was washed with Et₂O and then extracted with CHCl₃ (3 × 30 mL). Finally, removal of the solvent gave IS-DIB A. IS-DIB B and C were prepared from pre-B and pre-C in the range of 60–70% yields, respectively, by the same procedure. The purity of IS-DIB A, B, and C was estimated to be nearly 90% by ¹H NMR spectroscopy, due to containing a trace amount of pre-A, pre-B, and pre-C, respectively. N-Methyl-N-[3-(4′-diacetoxyiodo)phenyl-1-propyl]-pyrrolidinium 4′′-Methylbenzenesulfonate (IS-DIB A): viscous oil. IR (neat): 1646, 1556, 1272, 799 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ (cation) = 2.00 (s, 6 H), 2.06–2.29 (m, 6 H), 2.78 (t, J = 7.8 Hz, 2 H), 3.14 (s, 3 H), 3.54–3.73 (m, 6 H), 7.36 (d, J = 8.6 Hz, 2 H), 7.99 (d, J = 8.6 Hz, 2 H); δ (anion TsO^–) = 2.35 (s, 3 H), 7.17 (d, J = 8.2 Hz, 2 H), 7.77 (d, J = 8.2 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 20.28, 21.50, 21.80, 25.27, 31.83, 48.34, 63.47, 64.33, 118.75, 125.68, 128.66, 131.08, 135.11, 139.61, 143.31, 144.49, 176.46. ESI-HMRS: m/z calcd for C₁₈H₂₇O₄NI [M⁺]: 448.0979; found: 448.0967. N-Methyl-N-[3-(4′-diacetoxyiodo)phenoxy-1-propyl]-pyrrolidinium 4′′-Methylbenzenesulfonate (IS-DIB B): viscous oil. IR (neat): 1650, 1583, 1275, 1010, 823 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ (cation) = 1.98 (s, 6 H), 2.18–2.29 (m, 6 H), 3.17 (s, 3 H), 3.59–3.74 (m, 6 H), 4.13 (t, J = 5.6 Hz, 2 H), 6.93 (d, J = 9.1 Hz, 2 H), 7.97 (d, J = 9.1 Hz, 2 H); δ (anion TsO^–) = 2.31 (s, 3 H), 7.12 (d, J = 8.2 Hz, 2 H), 7.73 (d, J = 8.2 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 20.28, 21.58, 22.03, 23.85, 48.46, 61.51, 64.51, 64.85, 111.67, 117.03, 125.66, 128.66, 137.02, 138.20, 143.32, 160.77, 176.43. ESI-HMRS: m/z calcd for C₁₈H₂₇O₅NI [M⁺]: 464.0928; found: 464.0919. 3-[4′-(Diacetoxyiodo)phenoxy]-1-propyl-N,N,N-tri-methylammonium 4′′-Methylbenzenesulfonate (IS-DIB C): viscous oil. IR (neat): 1650, 1243, 1040, 812 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 1.98 (s 6 H), 2.30–2.35 (m 2 H), 3.28 (s, 9 H), 3.67 (t, J = 8.4 Hz, 2 H), 4.13 (t, J = 5.5 Hz, 2 H), 6.96 (d, J = 9.1 Hz, 2 H), 8.00 (d, J = 9.1 Hz, 2 H); δ (anion TsO^–) = 2.31 (s, 3 H), 7.12 (d, J = 8.2 Hz, 2 H), 7.71 (d, J = 8.2 Hz, 2 H). ¹³C NMR (100 MHz, CDCl₃): δ = 20.24, 21.43, 23.03, 53.44, 64.12, 64.68, 111.79, 116.98, 126.35, 129.23, 137.09, 138.19, 142.44, 160.76, 176.63. ESI-HMRS: m/z calcd for C₁₆H₂₅NI [M⁺]:438.0772; found: 438.0760
• 9 McKillop A, Kemp D. Tetrahedron 1989; 45: 3299
• 10 General Procedure for the Oxidation of Alcohols with IS-DIB A, B, and C in the Presence of TEMPO: To a solution of IS-DIB A, B, or C (1.5 equiv, 0.75 mmol) in CH₂Cl₂ (2 mL) were added alcohol (0.5 mmol) and TEMPO (10 mol%, 0.05 mmol). Then, the reaction mixture was stirred for 2 h at r.t. Then, the reaction mixture was concentrated in vacuo, H₂O (20 mL) was added to the residue, and the aqueous layer was extracted with Et₂O (3 × 20 mL). The organic layer was dried over Na₂SO₄. Removal of the solvent under reduced pressure afforded the product (ketone or aldehyde), and purity of the product was estimated by ¹H NMR spectroscopy. On the other hand, the aqueous layer was extracted with CHCl₃ three times (3 × 20 mL). Then, the organic layer was washed with aq Na₂SO₃ and brine. The organic layer was dried over Na₂SO₄, and removal of the solvent under reduced pressure afforded ion-supported iodobenzene (recovery rate: 75–90%). Typical Procedure for the Regeneration of N-methyl-N-[3-(4′-diacetoxyiodo)phenyl-1-propyl]pyrrolidinium 4′′-Methylbenzenesulfonate (IS-DIB A): To a solution of N-methyl-N-[3-(4′-iodophenyl)-1-propyl]pyrrolidinium 4′′-methylbenzenesulfonate (5 mmol, 2.50 g) in AcOH (50 mL) was added portionwise NaBO₃·4H₂O (10 equiv, 50 mmol, 7.69 g). The mixture was stirred for 15 h at 45 °C. After the reaction, the reaction mixture was concentrated, and H₂O (20 mL) was added to the residue. Then the aqueous solution was washed with H₂O once, and then extracted with CHCl₃ five times (3 × 30 mL). The organic layer was dried over Na₂SO₄. Then, removal of the solvent at 45 °C under reduced pressure afforded N-methyl-N-[3-(4′-diacetoxy-iodo)phenyl-1-propyl]pyrrolidinium 4′′-methylbenzene-sulfonate (TsO^–/AcO^– = 1:1). The counteranion was completely converted into the tosylate anion by the stirring treatment of the obtained IS-DIB A with PTSA·H₂O (1.0 equiv) in MeCN (20 mL) at r.t. overnight. Then the solvent was removed and, and H₂O (20 mL) was added to the residue. The aqueous layer was washed with Et₂O and then extracted with CHCl₃ (3 × 30mL). Finally, removal of the solvent gave the regenerated IS-DIB A. Regenerated IS-DIB B and C were prepared from recovered N-methyl-N-[3-(4′-iodophenoxy)-1-propyl]pyrrolidinium 4′′-methylbenzenesulfonate (pre-B), and N-[3-(4′-iodophenoxy)-1-propyl]-N,N,N-trimethylammonium 4′′-methylbenzenesulfonate (pre-C), respectively, by the same method and conditions. Most of ketones and aldehydes in the present study are commercially available, and they are identified with authentic samples, except for the following products. 1-(5′-Methylfuran-2′-yl)-1-pentanone (2d): oil. IR (neat): 3121, 2931, 2827, 1671, 1518, 1452, 876 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 0.94 (t, J = 7.5 Hz, 3 H), 1.39 (sext, J = 7.5 Hz, 2 H), 1.69 (quin, J = 7.5 Hz, 2 H), 2.39 (s, 3 H), 2.75 (t, J = 7.5 Hz, 2 H), 6.14 (d, J = 3.4 Hz, 1 H), 7.09 (d, J = 3.4 Hz, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 13.15, 13.33, 21.76, 26.11, 37.17, 108.10, 118.22, 150.84, 156.84, 188.40. ESI-HMRS: m/z calcd for C₁₀H₁₅O₂ [M + H]: 167.1067; found: 167.1065. 1-Adamantanecarboxaldehyde (2m): mp 140–142 °C (lit.[11] mp 146–148 °C). IR (Nujol): 2815, 2698, 1722 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 1.68–1.80 (m, 12 H), 2.03–2.09 (m, 3 H), 9.32 (s, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 27.31, 35.80, 36.52, 44.82, 206.09. 8-(4′-Methylbenzenesulfonyloxy)octanal (2n): oil. IR (neat): 2859, 2723, 1723, 1359, 1176 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 1.21–1.36 (m, 6 H), 1.54–1.58 (m, 4 H), 2.41 (t, J = 7.4 Hz, 2 H), 2.45 (s, 3 H), 4.02 (t, J = 6.5 Hz, 2 H), 7.35 (d, J = 8.2 Hz, 2 H), 7.78 (d, J = 8.2 Hz, 2 H), 9.73–9.76 (m, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 21.43, 21.65, 24.95, 28.45, 28.52, 28.67, 43.58, 70.38, 127.67, 129.66, 132.96, 144.54, 202.50. ESI-HMRS: m/z calcd for C₁₅H₂₃O₄S [M + H]: 299.1312; found: 299.1310. 4-[(tert-Butyldimethylsilyl)oxy]cyclohexanone (2p): oil (commercial, oil). IR (neat): 1720 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 0.10 (s, 6 H), 0.92 (s, 9 H), 1.83–2.02 (m, 4 H), 2.18–2.28 (m, 2 H), 2.61–2.73 (m, 2 H), 4.10–4.17 (m, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = –5.39, 17.53, 25.24, 33.65, 36.38, 65.39, 211.26. HMRS (APPI): m/z calcd for C₁₂H₂₅O₂Si [M + H]: 229.1618; found: 229.1617. 2,3,4,6-Tetra-O-benzyl-d-glucono-1,5-lactone (2r): oil. IR (neat): 2919, 2869, 1755, 1454, 1165, 1094, 738, 698 cm^–1. ¹H NMR (400 MHz, CDCl₃): δ = 3.64–3.75 (m, 2 H), 3.88–3.98 (m, 2 H), 4.12 (d, J = 6.1 Hz, 1 H), 4.43–4.76 (m, 8 H), 4.98 (d, J = 11.3 Hz, 1 H), 7.15–7.41 (m, 20 H). ¹³C NMR (100 MHz, CDCl₃): δ = 68.21, 73.52, 73.69 (2 C), 73.91, 76.01, 78.12, 80.92, 127.79 (3 C), 127.91, 127.96 (3 C), 128.08, 128.37, 128.41 (2 C), 128.45, 136.90, 137.46 (2 C), 137.55, 169.31. ESI-HMRS: m/z calcd for C₃₄H₃₅O₆ [M + H]: 539.2428; found: 539.2423
• 11 Pelletier G, Bechara WS, Charette AB. J. Am. Chem. Soc. 2010; 132: 12817