A New Application of Hypervalent Iodine (λ5) Reagents with Organosulfonic Acids for Direct α-Organosulfonyloxylation Carbonyl Compounds

Ulhas S. Mahajan; Krishnacharya G. Akamanchi

doi:10.1055/s-2008-1072508

LETTER

A New Application of Hypervalent Iodine (λ⁵) Reagents with Organosulfonic Acids for Direct α-Organosulfonyloxylation Carbonyl Compounds

Ulhas S. Mahajan, Krishnacharya G. Akamanchi*
Department of Pharmaceutical Sciences & Technology, Institute of Chemical Technology, Matunga, Mumbai 400 019, India
Fax: +91(22)24145614; e-Mail: kgap@rediffmail.com;

Abstract

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Abstract

Hypervalent iodine (λ⁵) reagents in combination with p-toluenesulfonic acid when reacted with ketones under reflux temperature in acetonitrile gave α-tosyloxy ketones in moderate to excellent yields. The reaction was developed further for both ketones and dicarbonyl compounds using Dess-Martin periodinane reagent in combination with p-toluenesulfonic acid and methanesulfonic acid, to give mono-α-tosyloxy and mono-α-mesyloxy products in very high to excellent yields.

Key words

hypervalent iodine reagents - Dess-Martin periodinane - carbonyl compounds - organosulfonic acids - α-organosulfonyloxylation

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References and Notes

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General Experimental Procedure for α-Organo-sulfonyloxylation
To a stirred suspension of Dess-Martin periodinane (3.5 g, 7.5 mmol) and organosulfonic acid (10 mmol) in MeCN (15 mL) was added the substrate (5 mmol) in one portion and the reaction mixture was refluxed until complete consumption of starting material (monitored by TLC). After completion of reaction MeCN was removed under reduced pressure. The residue obtained was diluted by adding CHCl₃ (50 mL) and washed with sat. solutions of NaHCO₃ (2 × 30 mL) and brine (50 mL). The organic layer was dried over anhyd Na₂SO₄ and concentrated under reduced pressure to give the crude α-organosulfonyloxylated product. Pure product was obtained after column chromatography (SiO₂, mesh size 60-120, eluent, EtOAc-hexane, 15:85).

Spectroscopic Data for Selected of α-Tosyloxylated and α-Mesyloxylated Products 2-Oxo-2-phenylethyl-4-Methanebenzenesulfonate (Entry 1) Solid; mp 90 °C (lit.^5d 90-91 °C). IR (KBr): 1180, 1360, 1715 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 2.45 (s, 3 H), 5.27 (s, 2 H), 7.23-7.88 (m, 5 H) ppm.
2-Oxo-2-phenylethyl Methanesulfonate (Entry 1) Solid; mp 76-77 °C (lit.^1a 76-78 °C). IR (KBr): ν_max = 1725 cm^-1. ¹H NMR (60 MHz, CDCl₃): δ = 3.20 (s, 3 H), 5.43 (s, 2 H), 7.12-8.12 (m, 5 H) ppm.
2-(4-Chlorophenyl)-2-oxo-ethyl 4-Methanebenzene-sulfonate (Entry 2) Solid; mp 123 °C (lit.^6g 125 °C). IR (KBr): 1190, 1360, 1700 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 2.46 (s, 3 H), 5.21 (s, 2 H), 7.35 (d, J = 8.4 Hz, 2 H), 7.45 (d, J = 8.6 Hz, 2 H), 7.80 (d, J = 8.6 Hz, 2 H), 7.84 (d, J = 8.4 Hz, 2 H) ppm.
2-(2,4-Dichlorophenyl)-2-oxo-ethyl Methanesulfonate (Entry 3) Solid; mp 87 °C. IR (KBr): ν_max = 1710 cm^-1. ¹H NMR (60 MHz, CDCl₃): δ = 3.24 (s, 3 H), 5.44 (s, 2 H), 7.22-7.83 (m, 3 H) ppm. ¹³C NMR (300 MHz, CDCl₃): δ = 37.65, 69.83, 128.90, 129.92, 130.46, 131.63, 136.10, 136.57, 190.74. Anal. Calcd (%) for C₉H₈Cl₂O₄S: C, 38.16; H, 2.82. Found: C, 38.15; H, 2.81.
2-(4-Nitrophenyl)-2-oxo-ethyl 4-Methanebenzene-sulfonate (Entry 4) Solid; mp 137 °C (lit.^6g 130-131 °C). IR (KBr): 1180, 1340, 1710 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 2.47 (s, 3 H), 5.25 (s, 2 H), 7.37 (d, J = 8.3 Hz, 2 H), 7.83 (d, J = 8.3 Hz, 2 H), 8.03 (d, J = 8.9 Hz, 2 H), 8.32 (d, J = 8.9 Hz, 2 H) ppm.
2-Oxo-2- p -tolylethyl 4-Methylbenzenesulfonate (Entry 5) Solid; mp 80 °C (lit.^6g 82-83 °C). IR (KBr): 1170, 1350, 1700 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 2.41 (s, 3 H), 2.45 (s, 3 H), 5.24 (s, 2 H), 7.26 (d, J = 8.1 Hz, 2 H), 7.35 (d, J = 8.2 Hz, 2 H), 7.74 (d, J = 8.1 Hz, 2 H), 7.86 (d, J = 8.2 Hz, 2 H) ppm.
2-Oxo-2- p -tolylethyl Methanesulfonate (Entry 5) IR (KBr): ν_max = 1710 cm^-1. ¹H NMR (60 MHz, CDCl₃): δ = 2.44 (s, 3 H), 3.28 (s, 3 H), 5.48 (s, 2 H), 7.28 (d, J = 8.33 Hz, 2 H), 7.77 (d, J = 8.33 Hz, 2 H) ppm. ¹³C NMR (300 MHz, CDCl₃): δ = 190.68, 145.65, 130.93, 129.77, 127.86, 70.22, 39.27, 21.83. Anal. Calcd (%) for C₁₀H₁₂O₄S: C, 52.63; H, 5.26. Found: C, 52.64; H, 5.25.
2-(4-Methoxyphenyl)-2-oxo-ethyl Methanesulfonate (Entry 6) Solid; mp 98 °C. IR (KBr): ν_max1710 cm^-1. ¹H NMR (60 MHz, CDCl₃): δ = 3.22 (s, 3 H), 3.88 (s, 3 H), 5.44 (s, 2 H), 7.28 (d, J = 7.8 Hz, 2 H), 7.74 (d, J = 7.8 Hz, 2 H) ppm. ¹³C NMR (300 MHz, CDCl₃): δ = 37.63, 70.35, 55.82, 114.24, 126.81, 129.86, 165.12, 190.92. Anal. Calcd (%) for C₁₀H₁₂O₅S: C, 49.18; H, 4.91. Found: C, 49.20; H, 4.92.
2-[2-Chloro-4 (4-chlorophenoxy)phenyl]-2-oxo-ethyl Methanesulfonate (Entry 7) White solid; mp 118-119 °C. IR (KBr): ν_max = 1715 cm^-1. ¹H NMR (60 MHz, CDCl₃): δ = 3.20 (s, 3 H), 5.44 (s, 2 H), 7.20-7.89 (m, 7 H) ppm. ¹³C NMR (300 MHz, CDCl₃): δ = 39.23, 73.64, 117.32, 121.62, 123.35, 124.14, 130.70, 130.73, 131.31, 132.32, 132.40, 158.12, 190.40. Anal. Calcd (%) for C₁₅H₁₃Cl₂O₅S: C, 47.87; H, 3.45. Found: C, 47.86; H, 3.42.
1-Oxo-1-phenylpropan-2-yl 4-Methanebenzenesulfonate (Entry 8) Solid; mp 68 °C (lit.^6g 68-69 °C). IR (KBr): 1170, 1370, 1700 cm^-1. ¹H NMR (400 MHz, CDCl₃): δ = 1.60 (d, J = 7.0 Hz, 3 H), 2.41 (s, 3 H), 5.79 (q, J = 7.0 Hz, 1 H), 7.29 (d, J = 8.1 Hz, 2 H), 7.46 (t, J = 7.2 Hz, 2 H), 7.60 (t, J = 7.2 Hz, 1 H), 7.75 (d, J = 7.2 Hz, 2 H), 7.88 (d, J = 8.1 Hz, 2 H) ppm.
2-(Furan-2-yl)-2-oxo-ethyl 4-Methanebenzensulfonate (Entry 9) Solid; mp 62 °C (lit.^5e 65-67 °C). IR (KBr): ν_max = 1670
cm^-1. ¹H NMR (60 MHz, CDCl₃): δ = 3.27 (s, 3 H), 5.53 (s, 1 H), 7.28-8.05 (m, 3 H) ppm.
2-Oxo-cyclohexyl 4-Methylbenzenesulfonate (Entry 10) Solid; mp 76 °C (lit.^5e 74-76 °C). IR (KBr): ν_max = 1744
cm^-1. ¹H NMR (60 MHz, CDCl₃): δ = 1.30-2.70 (m, 11 H), 4.82 (s, 1 H), 7.10 (d, 2 H), 8.02 (d, 2 H) ppm.
2-Oxo-propyl Methanesulfonate (Entry 11) Oil.^1a IR (neat): ν_max = 1738, 1367, 1187 cm^-1. ¹H NMR (60 MHz, CDCl₃): δ = 2.20 (s, 3 H), 3.16 (s, 3 H), 4.37 (s, 2 H) ppm.
Ethyl 2-(Methylsulfonyloxy)-3-oxo-3-phenylpropanoate (Entry 15) Yellow oil.^1a IR (KBr): ν_max = 1670 cm^-1. ¹H NMR (60 MHz, CDCl₃): δ = 1.13 (t, 3 H), 3.23 (s, 3 H), 4.24 (q, 2 H), 6.23 (s, 1 H), 7.23-8.20 (m, 5 H) ppm.