Copper-Catalyzed One-Pot Synthesis of Functionalized 1,4-Dihydroazete Derivatives from Sulfonyl Azides, Terminal Alkynes, and Tetramethylguanidine

Issa Yavari; Manijeh Nematpour

doi:10.1055/s-0032-1317075

Synlett, Table of Contents

Synlett 2012; 23(15): 2215-2218
DOI: 10.1055/s-0032-1317075

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Copper-Catalyzed One-Pot Synthesis of Functionalized 1,4-Dihydroazete Derivatives from Sulfonyl Azides, Terminal Alkynes, and Tetramethylguanidine

Issa Yavari*

Department of Chemistry, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran, Fax: +98(21)82883455 Email: yavarisa@modares.ac.ir

,

Manijeh Nematpour

Department of Chemistry, Tarbiat Modares University, PO Box 14115-175, Tehran, Iran, Fax: +98(21)82883455 Email: yavarisa@modares.ac.ir

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Abstract

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Abstract

Ketenimine intermediates generated by the addition of copper acetylides to sulfonyl azides are trapped by tetramethylguanidine to afford 1,4-dihydro-N,N-dimethyl-3-aryl(alkyl)-4-aryl(alkyl)sulfoniminoazet-2-amine derivatives in moderate to good yields.

Key words

1,4-dihydroazete - copper iodide - tetramethylguanidine - sulfonyl azide - terminal alkyne - ketenimine

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References

References and Notes
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21 General Procedure for the Synthesis of Compounds 4
To a mixture of sulfonyl azide 2, (1.2 mmol), alkyne 1 (1 mmol), and CuI (0.1 mmol), Et₃N (1 mmol) in THF (2 mL) was slowly added tetramethylguanidine (1 mmol). The mixture was stirred at r.t. After completion of the reaction [about 12 h; TLC (EtOAc–hexane = 1:5) monitoring], the mixture was diluted with CH₂Cl₂ (2 mL) and aq NH₄Cl solution (3 mL), stirred for 30 min, and the layers were separated. The aqueous layer was extracted with CH₂Cl₂ (3 × 3 mL), and the combined organic fractions were dried (Na₂SO₄) and concentrated under reduced pressure. The residue was purified by flash column chromatography [silica gel (230–400 mesh; Merck), hexane–EtOAc = 5:1] to give the product. 1,4-Dihydro-N,N-dimethyl-3-phenyl-4-tosyliminoazet-2-amine (4a) Yellow oil; yield 0.27 g (80%). IR (KBr): ν_max = 3438, 2923, 1511, 1396, 1270, 1139, 1083 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 2.38 (3 H, s, Me), 2.80 (6 H, s, NMe₂), 3.94 (1 H, s, NH), 7.18 (2 H, t, ³ J = 7.5 Hz, Ar), 7.24 (1 H, t, ³ J = 7.5 Hz, Ar), 7.25–7.28 (4 H, m, Ph), 7.76 (2 H, d, ³ J = 7.9 Hz, Ar). ¹³C NMR (125.7 MHz, CDCl₃): δ = 29.7 (Me), 40.5 (NMe₂), 88.3 (C), 125.7 (CH), 126.4 (2 CH), 128.1 (2 CH), 128.7 (2 CH), 129.6 (2 CH), 137.5 (C), 141.1 (C), 142.3 (C), 166.1 (C), 169.2 (C). MS (EI): m/z (%) = 341 (2) [M⁺], 297 (8), 271 (12), 155 (100), 145 (22), 91 (70), 77 (54). Anal. Calcd (%) for C₁₈H₁₉N₃O₂S (341.00): C, 63.32; H, 5.61; N, 12.31. Found: C, 63.79; H, 5.54; N, 12.38. 1,4-Dihydro-N,N-dimethyl-3-phenyl-4-benzenesulfoniminoazet-2-amine (4b) Yellow oil; yield 0.27 g (82%). IR (KBr): ν_max = 3437, 2929, 1520, 1400, 1273, 1142, 1087 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 2.85 (6 H, s, NMe₂), 3.98 (1 H, s, NH), 7.15 (2 H, t, ³ J = 7.5 Hz, Ar), 7.20 (1 H, t, ³ J = 7.5 Hz, Ar), 7.23 (2 H, d, ³ J = 7.5 Hz, Ar), 7.25–7.29 (3 H, m, Ph), 7.78 (2 H, d, ³ J = 7.9 Hz, Ar). ¹³C NMR (125.7 MHz, CDCl₃): δ = 40.6 (NMe₂), 88.5 (C), 125.6 (CH), 126.5 (2 CH), 128.3 (2 CH), 128.8 (2 CH), 129.7 (2 CH), 137.5 (CH), 140.2 (C), 142.5 (C), 165.7 (C), 170.8 (C). MS (EI): m/z (%) = 327 (3) [M⁺], 283 (12), 257 (17), 145 (31), 141 (100), 77 (54). Anal. Calcd (%) for C₁₇H₁₇N₃O₂S (327.05): C, 62.36; H, 5.23; N, 12.83. Found: C, 62.06; H, 5.18; N, 12.75. 1,4-Dihydro-N,N-dimethyl-3-phenyl-4-methanesulfoniminoazet-2-amine (4c) Yellow oil; yield 0.20 g (74%). IR (KBr): ν_max = 3435, 2925, 1531, 1401, 1271, 1120 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 2.81 (3 H, s, Me), 2.93 (6 H, s, NMe₂), 4.01 (1 H, s, NH), 7.26 (2 H, t, ³ J = 7.4 Hz, Ar), 7.30 (1 H, t, ³ J = 7.4 Hz, Ar), 7.42 (2 H, d, ³ J = 7.4 Hz, Ar). ¹³C NMR (125.7 MHz, CDCl₃): δ = 29.2 (Me), 40.4 (NMe₂), 87.2 (C), 124.4 (CH), 125.7 (2 CH), 126.4 (2 CH), 140.9 (C), 162.3 (C), 172.5 (C). MS (EI): m/z (%) = 265 (2) [M⁺], 221 (10), 195 (14), 145 (30), 79 (100), 77 (44). Anal. Calcd (%) for C₁₂H₁₅N₃O₂S (265.00): C, 54.32; H, 5.70; N, 15.06. Found: C, 54.66; H, 5.64; N, 15.16. 1,4-Dihydro-N,N-dimethyl-3-propyl-4-tosyliminoazet-2-amine (4d) Yellow oil; yield 0.20 g (67%). IR (KBr): ν_max = 3436, 2924, 1510, 1397, 1271, 1138, 1084 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 0.87 (3 H, t, ³ J = 6.9 Hz, Me), 1.57–1.62 (2 H, m, CH₂), 2.38 (3 H, s, Me), 2.52 (2 H, t, ³ J = 7.0 Hz, CH₂), 2.91 (6 H, s, NMe₂), 3.94 (1 H, s, NH), 7.24 (2 H, d, ³ J = 8.0 Hz, Ar), 7.81 (2 H, d, ³ J = 8.0 Hz, Ar). ¹³C NMR (125.7 MHz, CDCl₃): δ = 13.8 (Me), 21.4 (CH₂), 22.7 (CH₂), 29.7 (Me), 40.5 (NMe₂), 86.1 (C), 126.5 (2 CH), 128.4 (2 CH), 139.0 (C), 142.0 (C), 166.6 (C), 172.5 (C). MS (EI): m/z (%) = 307 (2) [M⁺], 263 (14), 197 (14), 155 (100), 111 (28), 91 (55), 77 (44), 43 (22). Anal. Calcd (%) for C₁₅H₂₁N₃O₂S (307.01): C, 58.61; H, 6.89; N, 13.67. Found: C, 58.89; H, 6.94; N, 13.54. 1,4-Dihydro-N,N-dimethyl-3-propyl-4-benzenesulfoniminoazet-2-amine (4e) Yellow oil; yield 0.17 g (60%). IR (KBr): ν_max = 3455, 2925, 1513, 1269, 1142, 1087 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 0.87 (3 H, t, ³ J = 7.0 Hz, Me), 1.57–1.60 (2 H, m, CH₂), 2.51 (2 H, t, ³ J = 7.0 Hz, CH₂), 2.89 (6 H, s, NMe₂), 3.93 (1 H, s, NH), 7.39 (1 H, t, ³ J = 8.0 Hz, Ar), 7.43 (2 H, t, ³ J = 8.0 Hz, Ar), 7.91 (2 H, d, ³ J = 8.0 Hz, Ar). ¹³C NMR (125.7 MHz, CDCl₃): δ = 13.9 (Me), 21.1 (CH₂), 22.8 (CH₂), 40.5 (NMe₂), 86.1 (C), 124.3 (CH), 125.6 (2 CH), 128.2 (2 CH), 135.7 (C), 162.9 (C), 172.4 (C). MS (EI): m/z (%) = 293 (3) [M⁺], 249 (13), 223 (8), 141 (100), 111 (18), 77 (34), 43 (35). Anal. Calcd (%) for C₁₄H₁₉N₃O₂S (293.00): C, 57.31; H, 6.53; N, 14.32. C, 57.16; H, 6.48; N, 14.21. 1,4-Dihydro-N,N-dimethyl-3-propyl-4-methanesulfoniminoazet-2-amine (4f) Yellow oil; yield 0.13 g (57%). IR (KBr): ν_max = 3436, 1518, 1269, 1142, 1086 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 0.86 (3 H, t, ³ J = 6.9 Hz, Me), 1.57–1.61 (2 H, m, CH₂), 2.50 (2 H, t, ³ J = 6.9 Hz, CH₂), 2.76 (3 H, s, Me), 2.90 (6 H, s, NMe₂) 3.92 (1 H, s, NH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 13.8 (Me), 19.1 (CH₂), 22.6 (CH₂), 29.6 (Me), 40.5 (NMe₂), 86.7 (C), 162.9 (C), 172.5 (C). MS (EI): m/z (%) = 231 (2) [M⁺], 187 (11), 161 (18), 119 (41), 79 (100), 43 (25). Anal. Calcd (%) for C₉H₁₇N₃O₂S (231.02): C, 46.73; H, 7.41; N, 18.17. Found: C, 47.02; H, 7.34; N, 18.08. 1,4-Dihydro-N,N-dimethyl-3-butyl-4-tosyliminoazet-2-amine (4g) Yellow oil; yield 0.20 g (62%). IR (KBr): ν_max = 3452, 2933, 1520, 1401, 1270, 1118 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 0.85 (3 H, t, ³ J = 6.9 Hz, Me), 1.23–1.27 (2 H, m, CH₂), 1.59–1.62 (2 H, m, CH₂), 2.40 (3 H, s, Me), 2.50 (2 H, t, ³ J = 7.0 Hz, CH₂), 2.85 (6 H, s, NMe₂), 3.97 (1 H, s, NH), 7.38 (2 H, d, ³ J = 8.0 Hz, Ar), 7.92 (2 H, d, ³ J = 8.0 Hz, Ar). ¹³C NMR (125.7 MHz, CDCl₃): δ = 13.9 (Me), 19.4 (CH₂), 22.4 (CH₂), 27.3 (CH₂), 30.4 (Me), 40.3 (NMe₂), 86.6 (C), 125.6 (2 CH), 128.2 (2 CH), 137.7 (C), 141.2 (C), 166.0 (C), 172.5 (C). MS (EI): m/z (%) = 321 (3) [M⁺], 277 (16), 251 (13), 155 (100), 125 (20), 91 (51), 77 (41), 57 (52). Anal. Calcd (%) for C₁₆H₂₃N₃O₂S (321.00): C, 59.78; H, 7.21; N, 13.07. Found: C, 59.51; H, 7.27; N, 13.18. 1,4-Dihydro-N,N-dimethyl-3-butyl-4-benzenesulfoniminoazet-2-amine (4h) Yellow oil; yield 0.17 g (57%). IR (KBr): ν_max = 3413, 2926, 1517, 1401, 1268, 1141, 1086 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 0.84 (3 H, t, ³ J = 6.9 Hz, Me), 1.24–1.28 (2 H, m, CH₂), 1.59–1.62 (2 H, m, CH₂), 2.49 (2 H, t, ³ J = 7.0 Hz, CH₂), 2.92 (6 H, s, NMe₂), 3.98 (1 H, s, NH), 7.26 (1 H, t, ³ J = 7.9 Hz, Ar), 7.39 (2 H, t, ³ J = 7.9 Hz, Ar), 7.80 (2 H, d, ³ J = 7.9 Hz, Ar). ¹³C NMR (125.7 MHz, CDCl₃): δ = 14.1 (Me), 20.0 (CH₂), 22.5 (CH₂), 27.3 (CH₂), 40.5 (NMe₂), 86.4 (C), 125.6 (CH), 128.7 (2 CH), 129.6 (2 CH), 138.6 (C), 167.3 (C), 172.5 (C). MS (EI): m/z (%) = 307 (3) [M⁺], 263 (12), 237 (10), 141 (100), 125 (29), 77 (35), 57 (50). Anal. Calcd (%) for C₁₅H₂₁N₃O₂S (307.00): C, 58.61; H, 6.89; N, 13.67. Found: C, 58.86; H, 6.74; N, 13.55. 1,4-Dihydro-N,N-dimethyl-3-butyl-4-methanesulfoniminoazet-2-amine (4i) Yellow oil; yield 0.13 g (53%). IR (KBr): ν_max = 3513, 2934, 1521, 1403, 1270, 1118, 1042 cm^–1. ¹H NMR (500 MHz, CDCl₃): δ = 0.85 (3 H, t, ³ J = 6.9 Hz, Me), 1.21–1.29 (2 H, m, CH₂), 1.62–1.66 (2 H, m, CH₂), 2.47 (2 H, t, ³ J = 7.0 Hz, CH₂), 2.82 (3 H, s, Me), 2.90 (6 H, s, NMe₂), 3.96 (1 H, s, NH). ¹³C NMR (125.7 MHz, CDCl₃): δ = 14.0 (Me), 19.8 (CH₂), 22.4 (CH₂), 27.3 (CH₂), 30.7 (Me), 40.4 (NMe₂), 86.2 (C), 166.2 (C), 172.6 (C). MS (EI): m/z (%) = 245 (2) [M⁺], 201 (12), 175 (10), 125 (39), 79 (100), 57 (46). Anal. Calcd (%) for C₁₀H₁₉N₃O₂S (245.00): C, 48.95; H, 7.81; N, 17.13. Found: C, 48.76; H, 7.75; N, 17.04
22 Recently, Sharpless and co-workers established anhydrous conditions with CuI in CHCl₃/2,6-lutidine at 0 °C to prevent intermediate 6 from decomposing and provide selective formation of the desired 1-sulfonyltriazoles: Yoo EJ, Ahlquist M, Kim SH, Bae I, Fokin VV, Sharpless KB, Chang S. Angew. Chem. Int. Ed. 2007; 46: 1730
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