Copper-Catalyzed Synthesis of Sulfenamides Utilizing Diaryl Disulfides with Alkyl Amines

Abstract

The copper-catalyzed coupling of diaryl disulfides with alkyl amines can afford various sulfenamides in good yields. Furthermore, the present reaction is efficient and can be used for both of the aryl sulfide groups on disulfide.

Key words

sulfenamide - copper catalyst - diaryl disulfide - alkyl­amine

References and Notes

• 1a Davis FA. J. Org. Chem.  2006,  71:  8993 
• 1b Craine L. Raban M. Chem. Rev.  1989,  89:  689 
• 2a Matsuo J.-i. Iida D. Tatani K. Mukaiyama T. Bull. Chem. Soc. Jpn.  2002,  75:  223 
• 2b Matsuo J.-i. Iida D. Yamanaka H. Mukaiyama T. Tetrahedron  2003,  59:  6739 
• 3a Kuniyasu H. Kato T. Asano S. Ye J.-H. Ohmori T. Morita M. Hiraike H. Fujiwara S.-i. Terao J. Kurosawa H. Kambe N. Tetrahedron Lett.  2006,  47:  1141 
• 3b Kondo T. Baba A. Nishi Y. Mitsudo T.-a. Tetrahedron Lett.  2004,  45:  1469 
• 3c Zyk NV. Beloglzkina EK. Gazzaeva R. Tyurin VS. Titanyuk ID. Phosphorus, Sulfur Silicon Relat. Elem.  1999,  155:  33 
• 4a Miura Y. Asada H. Kinoshita M. Bull. Chem. Soc. Jpn.  1977,  50:  1855 
• 4b Heimer NE. Field L. J. Org. Chem.  1970,  35:  3012 
• 5a Davis FA. Friedman AJ. Kluger EW. Skibo EB. Fretz ER. Milicia AP. LeMasters WC. Bentley MD. Lacadie JA. Douglass IB. J. Org. Chem.  1977,  42:  967 
• 5b Davis FA. Slgeir WAR. Evans S. Schwartz A. Goff DL. Palmer R. J. Org. Chem.  1973,  38:  2809 
• Intramolecular S-N bond formation is also reported:
• 6a Correa A. Tellitu I. Domínguez E. SanMartin R. Org. Lett.  2006,  8:  4811 
• 6b Jin CK. Moon J.-K. Lee WS. Nam KS. Synlett  2003,  1967 
• 7 Taniguchi N. J. Org. Chem.  2004,  69:  915 
• 8a Taniguchi N. Synlett  2006,  1351 
• 8b Taniguchi N. J. Org. Chem.  2007,  72:  1241 
• 8c Taniguchi N. J. Org. Chem.  2006,  71:  7874 
• 11 Adams R. Reifschneider W. Ferretti A. Org. Synth., Coll. Vol. V   John Wiley & Sons; New York: 1973.  p.107-110  

9

Typical Procedure
To a mixture of CuI (9.5 mg, 0.05 mmol), TMEDA (5.8 mg, 0.05 mmol), and DMSO (0.3 mL) were added (PhS)₂ (109.2 mg, 0.5 mmol) and Et₂NH (76.8 mg, 1.05 mmol), and the mixture was stirred at 65 °C for 18 h in air. After the residue was dissolved in Et₂O, the solution was washed with H₂O and sat. NaCl and dried over anhyd MgSO₄. The crude product was distilled (140 °C/30 Pa) to give N-(phenylthio)-N,N-diethylamine (134.8 mg, 74%).^5a N -(Phenylthio)- N , N -diethylamine
IR (neat): 2970, 2847, 1582, 1475, 1438, 1374 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.34-7.25 (m, 4 H), 7.15-7.08 (m, 1 H), 3.00 (q, J = 7.1 Hz, 4 H), 1.18 (t, J = 7.1 Hz, 6 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 141.2, 128.4, 125.3, 125.0, 52.1, 13.7. Anal. Calcd for C₁₀H₁₅NS: C, 66.25; H, 8.34; N, 7.73. Found: C, 65.92; H, 8.02; N, 7.80.
N -(Phenylthio)pyrrolidine
IR (neat): 2967, 2845, 1582, 1475, 1438 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.31-7.27 (m, 4 H), 7.18-7.14 (m, 1 H), 3.13-3.09 (m, 4 H), 1.87-1.82 (m, 4 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 139.4, 128.6, 126.3, 125.9, 55.2, 25.6. Anal. Calcd for C₁₀H₁₃NS: C, 66.99; H, 7.31; N, 7.81. Found: C, 66.70; H, 7.24; N, 7.84.
N -(Phenylthio)- N -(methyl)aminoethanol
IR (neat) 3391, 2940, 2880, 1582, 1476, 1438 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.40-7.23 (m, 5 H), 3.77 (t, J = 5.1 Hz, 2 H), 3.02 (t, J = 5.1 Hz, 2 H), 2.87 (s, 3 H), 2.00 (br, 1 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 136.3, 129.4, 128.8, 127.5, 60.8, 59.9, 47.3. Anal. Calcd for C₉H₁₃NS: C, 58.98; H, 7.15; N, 7.64. Found: C, 59.17; H, 7.11; N, 7.24.
N -(Phenylthio)- N -butylamine
IR (neat): 3338, 2957, 2929, 1582, 1476, 1438 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.34-7.24 (m, 4 H), 7.15-7.10 (m, 1 H), 2.93 (q, J = 6.9 Hz, 2 H), 2.80 (br, 1 H), 1.56-1.50 (m, 2 H), 1.48-1.31 (m, 2 H), 0.90 (t, J = 7.2 Hz, 3 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 141.9, 128.7, 125.2, 123.8, 51.9, 32.5, 20.0, 13.9. Anal. Calcd for C₁₀H₁₅NS: C, 66.25; H, 8.34; N, 7.73. Found: C, 66.46; H, 8.05; N, 7.70.
N -(Phenylthio)- N -(tert -butyl)amine ^4a,5a
IR (neat): 3327, 2969, 1582, 1476, 1361 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.34 (d, J = 7.6 Hz, 2 H), 7.26 (t, J = 7.6 Hz, 2 H), 7.05 (t, J = 7.6 Hz, 1 H), 2.78 (br, 1 H), 1.17 (s, 9 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 144.4, 128.4, 124.4, 122.4, 54.7, 29.2. Anal. Calcd for C₁₀H₁₅NS: C, 66.25; H, 8.34; N, 7.73. Found: C, 65.98; H, 8.20; N, 7.54.

10

N -(2-Methylphenylthio)- N , N -diethylamine IR (neat): 2970, 2849, 1589, 1463, 1378 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.50 (d, J = 7.9 Hz, 1 H), 7.15 (t, J = 7.9 Hz, 1 H), 7.07-6.97 (m, 2 H), 3.05 (q, J = 7.0 Hz, 4 H), 2.20 (s, 3 H), 1.17 (t, J = 7.0 Hz, 6 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 141.2, 131.6, 129.7, 125.8, 124.0, 122.8, 52.1, 18.5, 13.5. Anal. Calcd for C₁₁H₁₇NS: C, 67.64; H, 8.77; N, 7.17. Found: C, 67.34; H, 8.71; N, 7.02.
N -(4-Methylphenylthio)- N , N -diethylamine
IR (neat): 2970, 2830, 1597, 1489, 1374 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.25 (d, J = 7.9 Hz, 2 H), 7.10 (d, J = 7.9 Hz, 2 H), 2.93, (q, J = 7.0 Hz, 4 H), 2.32 (s, 3 H), 1.19 (t, J = 7.0 Hz, 6 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 136.0, 135.8, 129.3, 127.3, 51.9, 21.0, 13.7. Anal. Calcd for C₁₁H₁₇NS: C, 67.64; H, 8.77; N, 7.17. Found: C, 67.51; H, 8.79; N, 7.22.
N -(4-Methoxylphenylthio)- N , N -diethylamine
IR (neat): 2971, 2835, 1590, 1492 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.36 (d, J = 8.7 Hz, 2 H), 6.87 (d, J = 8.7 Hz, 2 H), 3.80 (s, 3 H), 2.81 (q, J = 7.0 Hz, 4 H), 1.21 (t, J = 7.0 Hz, 6 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 159.5, 132.8, 126.9, 114.1, 55.3, 51.4, 13.7. Anal. Calcd for C₁₁H₁₇NOS: C, 62.52; H, 8.11; N, 6.63. Found: C, 62.47; H, 8.03; N, 6.42.
N -(2-Methylphenylthio)- N -(tert -butyl)amine
IR (neat): 3322, 2969, 1589, 1463, 1361 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.65 (d, J = 7.9 Hz, 1 H), 7.18, (t, J = 7.9 Hz, 1 H), 7.05-6.95 (m, 2 H), 2.60 (br, 1 H), 2.23 (s, 3 H), 1.19 (s, 9 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 142.5, 131.5, 129.5, 125.9, 123.9, 122.4, 54.6, 29.2, 18.5. Anal. Calcd for C₁₁H₁₇NS: C, 67.64; H, 8.77; N, 7.17. Found: C, 67.54; H, 8.79; N, 6.97.
N -(4-Methylphenylthio)- N -(tert -butyl)amine
IR (neat): 3325, 2969, 1598, 1490, 1361 cm^-1. ¹H NMR (270 MHz, CDCl₃): δ = 7.25 (d, J = 8.2 Hz, 2 H), 7.08 (d, J = 8.2 Hz, 2 H), 2.80 (br, 1 H), 2.30 (s, 3 H), 1.17 (s, 9 H). ¹³C NMR (67.5 MHz, CDCl₃): δ = 140.8, 134.3, 129.2, 122.9, 54.8, 29.2, 20.9. Anal. Calcd for C₁₁H₁₇NS: C, 67.64; H, 8.77; N, 7.17. Found: C, 67.35; H, 8.71; N, 6.92.