A Facile Aerobic Copper-Catalyzed α-Oxygenation of Aryl Thioacetamides: An Efficient Access to α-Keto Aryl Thioamides

Firouz Matloubi Moghaddam; Zohreh Mirjafary; Hamdollah Saeidian; Marjan Jebeli Javan

doi:10.1055/s-2008-1042925

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Synlett 2008(6): 892-896
DOI: 10.1055/s-2008-1042925

LETTER

A Facile Aerobic Copper-Catalyzed α-Oxygenation of Aryl Thioacetamides: An Efficient Access to α-Keto Aryl Thioamides

Firouz Matloubi Moghaddam*, Zohreh Mirjafary, Hamdollah Saeidian, Marjan Jebeli Javan
Laboratory of Organic Synthesis & Natural Products, Department of Chemistry, Sharif University of Technology, P. O. Box 11155-9516, Tehran, Iran
e-Mail: matloubi@sharif.edu;

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Publication History

Received 17 December 2007
Publication Date:
11 March 2008 (online)

Abstract
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Abstract

Copper(II) efficiently catalyzes the aerobic oxidation of aryl thioacetamides into the corresponding α-keto aryl thioamides in moderate to high yields in the presence of K₂CO₃ under O₂ atmosphere. This protocol is simple, clean, and generates water as the only byproduct. A mechanism is proposed for the reaction course.

Key words

CuCl₂·2H₂O - oxygenation - α-keto aryl thioamides - thioacetomorpholides

References and Notes

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12

Spectral Data of the Products Compound 2a: ¹H NMR (500 MHz, CDC1₃): δ = 7.93 (d, J = 7.18 Hz, 2 H), 7.55 (t, J = 7.41 Hz, 1 H), 7.43 (t, J = 7.76 Hz, 2 H), 4.27 (t, J = 4.94 Hz, 2 H), 3.84 (t, J = 4.95 Hz, 2 H), 3.63 (t, J = 4.77 Hz, 2 H), 3.53 (t, J = 4.76 Hz, 2 H) ppm. ¹³C NMR (125 MHz, CDC1₃): δ = 196.16, 188.31, 134.86, 133.70, 130.27, 129.38, 66.93, 66.81, 52.35, 47.54 ppm. MS (EI): m/z (%) = 235 (73) [M⁺], 177 (30), 130 (100), 105 (53), 86 (71), 77 (46). Anal Calcd for C₁₂H₁₃NO₂S: C, 61.25; H, 5.57; N, 5.95. Found: 61.59; H, 5.72; N, 5.94.
Compound 2b: ¹H NMR (500 MHz, CDC1₃): δ = 7.82 (d, J = 8.21 Hz, 2 H), 7.22 (t, J = 8.11 Hz, 2 H), 4.26 (t, J = 4.95 Hz, 2 H), 3.83 (t, J = 4.95 Hz, 2 H), 3.62 (t, J = 4.77 Hz, 2 H), 3.53 (t, J = 4.71 Hz, 2 H), 2.36 (s, 3 H) ppm. ¹³C NMR (125 MHz, CDC1₃): δ = 196.47, 188.30, 146.13, 131.19, 130.40, 130.10, 66.93, 66.81, 52.32, 47.51, 22.29 ppm.
Compound 2c: ¹H NMR (500 MHz, CDC1₃): δ = 7.88 (d, J = 8.80 Hz, 2 H), 6.87 (d, J = 8.82 Hz, 2 H), 4.24 (t, J = 4.23 Hz, 2 H), 3.81 (t, J = 4.63 Hz, 2 H), 3.80 (s, 3 H), 3.60 (t, J = 4.02 Hz, 2 H), 3.51 (s, 2 H) ppm. ¹³C NMR (125 MHz, CDC1₃): δ = 196.54, 188.31, 165.07, 132.73, 126.46, 114.73, 66.95, 66.79, 56.10, 52.33, 47.57 ppm.
Compound 2d: ¹H NMR (500 MHz, CDC1₃): δ = 7.79 (d, J = 8.40 Hz, 2 H), 7.56 (d, J = 8.40 Hz, 2 H), 4.24 (t, J = 4.87 Hz, 2 H), 3.80 (t, J = 4.90 Hz, 2 H), 3.63 (t, J = 4.75 Hz, 2 H), 3.52 (t, J = 4.65 Hz, 2 H) ppm. ¹³C NMR (125 MHz, CDC1₃): δ = 195.49, 185.86, 141.22, 132.30, 131.49, 129.55, 66.90, 66.72, 52.33, 47.58 ppm.
Compound 2e: ¹H NMR (500 MHz, CDC1₃): δ = 7.94 (d, J = 8.56 Hz, 2 H), 7.46 (d, J = 8.52 Hz, 2 H), 4.31 (t, J = 4.95 Hz, 2 H), 3.89 (t, J = 4.95 Hz, 2 H), 3.69 (t, J = 4.82 Hz, 2 H), 3.58 (t, J = 4.82 Hz, 2 H) ppm. ¹³C NMR (125 MHz, CDC1₃): δ = 195.54, 186.76, 141.38, 132.34, 131.57, 129.69, 66.92, 66.75, 52.35, 47.61 ppm. Anal. Calcd for C₁₂H₁₂ClNO₂S: C, 53.43; H, 4.48; N, 5.19. Found: C, 53.44; H, 4.44; N, 5.08.
Compound 2f: ¹H NMR (500 MHz, CDC1₃): δ = 8.00 (d, J = 6.81 Hz, 2 H), 7.65 (d, J = 8.38 Hz, 2 H), 7.56 (d, J = 7.20 Hz, 2 H), 7.42 (t, J = 6.53 Hz, 2 H), 7.37 (t, J = 5.28 Hz, 1 H), 4.29 (t, J = 4.93 Hz, 2 H), 3.86 (t, J = 4.93 Hz, 2 H), 3.66 (t, J = 4.71 Hz, 2 H), 3.58 (t, J = 4.63 Hz, 2 H) ppm. ¹³C NMR (125 MHz, CDC1₃): δ = 196.20, 187.97, 147.64, 139.98, 132.42, 130.87, 129.48, 129.02, 128.04, 127.76, 66.99, 66.63, 52.40, 47.59 ppm.
Compound 2g: ¹H NMR (500 MHz, CDC1₃): δ = 8.81 (d, J = 4.68 Hz, 2 H), 7.79 (d, J = 4.79 Hz, 2 H), 4.27 (t, J = 4.33 Hz, 2 H), 3.88 (t, J = 4.40 Hz, 2 H), 3.69 (t, J = 4.23 Hz, 2 H), 3.57 (t, J = 4.41 Hz, 2 H) ppm. ¹³C NMR (125 MHz, CDC1₃): δ = 193.71, 185.27, 150.79, 140.28, 123.01, 66.90, 66.73, 52.41, 47.69 ppm.
Compound 2h: ¹H NMR (500 MHz, CDC1₃): δ = 9.21 (d, J = 8.70 Hz, 1 H), 8.07 (d, J = 8.15 Hz, 1 H), 8.02 (d, J = 7.10 Hz, 1 H), 7.90 (d, J = 8.15 Hz, 1 H), 7.69 (t, J = 7.40 Hz, 1 H), 7.58 (t, J = 7.50 Hz, 1 H), 7.50 (t, J = 7.72 Hz, 1 H), 4.37 (t, J = 4.86 Hz, 2 H), 3.42 (t, J = 4.87 Hz, 2 H), 3.71-3.69 (m, 4 H) ppm. ¹³C NMR (125 MHz, CDC1₃): δ = 197.38, 189.76, 135.85, 134.62, 133.27, 131.93, 129.84, 129.55, 129.14, 127.37, 126.48, 124.66, 66.91, 66.79, 52.47, 47.88 ppm.
Compound 2i: ¹H NMR (500 MHz, CDC1₃): δ = 8.54 (s, 1 H), 7.97 (d, J = 8.52 Hz, 1 H), 7.90 (d, J = 8.15 Hz, 1 H), 7.86 (d, J = 8.62 Hz, 1 H), 7.82 (d, J = 8.09 Hz, 1 H), 7.57 (t, J = 7.47 Hz, 1 H), 7.50 (t, J = 7.53 Hz, 1 H), 4.32 (t, J = 4.89 Hz, 2 H), 3.87 (t, J = 4.90 Hz, 2 H), 3.63 (t, J = 4.54 Hz, 2 H), 3.57 (t, J = 4.28 Hz, 2 H) ppm. ¹³C NMR (125 MHz, CDC1₃): δ = 196.25, 188.46, 136.61, 132.94, 132.85, 131.04, 130.27, 129.78, 129.39, 128.36, 127.60, 124.76, 66.98, 66.85, 52.44, 47.67 ppm.
Compound 2j: ¹H NMR (500 MHz, CDC1₃): δ = 10.11 (s, 1 H), 8.15 (d, J = 8.28 Hz, 2 H), 7.99 (d, J = 8.25 Hz, 2 H), 4.34 (t, J = 4.93 Hz, 2 H), 3.92 (t, J = 4.95 Hz, 2 H), 3.71 (t, J = 5.23 Hz, 2 H), 3.62 (t, J = 5.15 Hz, 2 H) ppm. ¹³C NMR (125 MHz, CDC1₃): δ = 194.98, 191.65, 186.43, 140.14, 138.34, 130.74, 130.30, 66.94, 66.79, 52.44, 47.69 ppm.
Compound 2k: ¹H NMR (500 MHz, CDC1₃): δ = 7.88 (d, J = 7.19 Hz, 2 H), 7.60 (t, J = 6.90 Hz, 1 H), 7.45 (t, J = 7.78 Hz, 2 H), 3.75-3.71 (m, 4 H), 3.59 (t, J = 2.82 Hz, 2 H), 3.31 (t, J = 4.82 Hz, 2 H) ppm. ¹³C NMR (125 MHz, CDC1₃):
δ = 191.56, 165.89, 135.37, 133.48, 130.10, 129.53, 67.16, 67.09, 46.70, 42.06 ppm.