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Synlett 2012; 23(8): 1250-1256
DOI: 10.1055/s-0031-1290766
letter
© Georg Thieme Verlag Stuttgart · New York

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

Yusuke Suzuki
Graduate School of Science, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan
,
Masataka Iinuma
Graduate School of Science, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan
,
Katsuhiko Moriyama
Graduate School of Science, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan
,
Hideo Togo*
Graduate School of Science, Chiba University, Yayoi-cho 1-33, Inage-ku, Chiba 263-8522, Japan
› Author Affiliations
Further Information

Publication History

Received: 31 January 2012

Accepted after revision: 15 February 2012

Publication Date:
20 April 2012 (online)

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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

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    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
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  • 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
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  • 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
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