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DOI: 10.1055/s-2008-1078405
Silver-Catalyzed Preparation of Oxazolines from N-Propargylamides
Publikationsverlauf
Publikationsdatum:
07. Mai 2008 (online)
Abstract
Treatment of N-propargylamides with 5 mol% of silver hexafluoroantimonate results in the rapid formation of oxazolines in essentially quantitative yield.
Key words
N-propargylamides - silver - oxazolines - catalysis
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References and Notes
Harmata, M.; Huang, C. Adv. Synth. Catal. 2008, 350, 972.
12
General Procedure for the Preparation of Methylene Oxazolines from N
-Propargylamides:
The amide (1 mmol) was placed in a dry flask with CH2Cl2 (2 mL). AgSbF6 (5 mol%) was added in one portion with magnetic stirring. After 5-10 min, TLC showed no starting material. The reaction mixture was filtered through Celite and washed with CH2Cl2. The filtrate was evaporated to afford the pure (1H NMR) product.
The starting amides were prepared by the reaction of amines with acid chlorides.
14The conversion of 8 into 9 required 15 min with 2% catalyst, 1 h with 1% catalyst and 28 h with 0.1% catalyst, all reactions being conducted at r.t.
15Data of selected compounds: 16: solid; mp 138-140 °C. 1H NMR (500 MHz, CDCl3): δ = 7.25-7.37 (m, 5 H), 5.55 (s, 1 H), 3.54 (s, 2 H), 2.31 (s, 1 H), 1.57 (s, 6 H). 13C NMR (125.8 MHz, CDCl3): δ = 169.9, 134.8, 129.2, 128.9, 127.2, 87.5, 69.1, 47.6, 44.4, 28.7. IR (CH2Cl2): 3309, 3215, 2099, 1642, 1540, 1221, 722 cm-1. HRMS: m/z calcd for C13H15NONa+: 224.1043; found: 224.1043. 17: solid; mp 192-193 °C. 1H NMR (500 MHz, CDCl3): δ = 7.26-7.34 (m, 5 H), 4.57 (d,
J = 3.0 Hz, 1 H), 4.14 (d, J = 3.0 Hz, 1 H), 3.69 (s, 2 H), 1.35 (s, 6 H). 13C NMR (125.8 MHz, CDCl3): δ = 167.7, 134.2, 128.8, 128.7, 127.1, 82.3, 68.5, 34.8, 29.4. IR (CH2Cl2): 2974, 2921, 1662, 1454, 1180, 1123 cm-1. HRMS: m/z calcd for C13H15NONa+: 224.1043; found: 224.1044. 18: solid; mp 96-97 °C. 1H NMR (500 MHz, CDCl3): δ = 5.65 (s, 1 H), 2.33 (s, 1 H), 2.17 (q, J = 12.5 Hz, 2 H), 1.64 (s, 6 H), 1.14 (t, J = 12.5 Hz, 3 H). 13C NMR (125.8 MHz, CDCl3): δ = 177.8, 87.3, 68.9, 47.4, 30.1, 28.9, 9.4. IR (CH2Cl2): 3309, 3223, 2982, 2238, 2099, 1658, 1540, 898, 718 cm-1. HRMS: m/z calcd for C8H13NONa+: 162.0889; found: 162.0887. 19: solid; mp 118-120 °C. 1H NMR (500 MHz, CDCl3): δ = 4.81 (d, J = 3.5 Hz, 1 H), 4.38 (d, J = 3.5 Hz, 1 H), 2.50 (q, J = 3.0 Hz, 2 H), 1.45 (s, 6 H), 1.32 (t, J = 3.0 Hz, 3 H). 13C NMR (125.8 MHz, CDCl3): δ = 171.6, 164.6, 86.0, 68.0, 30.1, 22.9, 9.7. IR (CH2Cl2): 3624, 3411, 2986, 1654, 1180, 665 cm-1. HRMS: m/z calcd for C8H13NOH+: 140.1070; found: 140.1068. 20: solid; mp 96-98 °C. 1H NMR (500 MHz, CDCl3): δ = 6.84 (dt, J = 9.0, 14.5 Hz, 1 H), 5.92 (s, 1 H), 5.81 (d, J = 14.5 Hz, 1 H), 2.34 (s, 1 H), 1.83 (d, J = 9.0 Hz, 3 H), 1.67 (s, 6 H). 13C NMR (125.8 MHz, CDCl3): δ = 165.0, 139.9, 125.3, 87.2, 68.9, 47.3, 28.9, 17.5. IR (CH2Cl2): 3293, 3239, 2974, 2108, 1634, 1540, 1233, 967 cm-1. HRMS: m/z calcd for C9H13NONa+: 174.0890; found: 174.0889. 21: oil. 1H NMR (500 MHz, CDCl3): δ = 6.84 (dt, J = 6.0, 15.5 Hz, 1 H), 6.07 (d, J = 15.5 Hz, 1 H), 4.72 (d,
J = 3.0 Hz, 1 H), 4.27 (d, J = 3.0 Hz, 1 H), 1.94 (d, J = 6.0 Hz, 3 H), 1.41 (s, 6 H). 13C NMR (125.8 MHz, CDCl3): δ = 165.9, 161.3, 143.3, 117.6, 83.5, 68.1, 29.8, 18.5. IR (CH2Cl2): 2970, 1674, 1307, 1184, 972, 661 cm-1. HRMS: m/z calcd for C9H13NONa+: 174.0889; found: 174.0886. 22: solid; mp 48-49 °C. 1H NMR (500 MHz, CDCl3): δ = 5.81 (s, 1 H), 3.61 (t, J = 6.0 Hz, 2 H), 2.34 (t, J = 6.0 Hz, 2 H), 2.11 (tt, J = 6.0, 6.0 Hz, 2 H), 1.64 (s, 6 H). 13C NMR (125.8 MHz, CDCl3): δ = 170.8, 86.9, 67.1, 47.5, 44.4, 33.5, 28.9, 27.9. IR (CH2Cl2): 3350, 3239, 2994, 2108, 1646, 1540, 1221 cm-1. HRMS: m/z calcd for C9H14ClNONa+: 210.0656; found: 210.0651. 23: oil. 1H NMR (500 MHz, CDCl3): δ = 4.60 (d, J = 3.0 Hz, 1 H), 4.10 (d, J = 3.0 Hz, 1 H), 3.63 (t,
J = 6.0 Hz, 2 H), 2.56 (t, J = 7.0 Hz, 2 H), 2.17 (tt, J = 6.0, 7.0 Hz, 2 H), 1.35 (s, 6 H). 13C NMR (125.8 MHz, CDCl3): δ = 167.5, 162.9, 82.2, 68.3, 43.8, 29.5, 28.2, 25.2. IR (CH2Cl2): 2974, 2929, 1679, 1192, 1127, 963 cm-1. HRMS: m/z calcd for C9H14ClNOH+: 188.0837; found: 188.1277. 24: solid; mp 106-107 °C. 1H NMR (500 MHz, CDCl3): δ = 5.67 (s, 1 H), 2.32 (s, 1 H), 1.66 (s, 6 H), 1.20 (s, 9 H). 13C NMR (125.8 MHz, CDCl3): δ = 177.4, 87.4, 68.8, 47.4, 38.9, 28.7, 27.4. IR (CH2Cl2): 3362, 3288, 2998, 1650, 1523, 1356, 1209 cm-1. HRMS: m/z calcd for C10H17NONa+: 190.1202; found: 190.1200. 25: oil. 1H NMR (500 MHz, CDCl3): δ = 4.56 (d, J = 2.5 Hz, 1 H), 4.10 (d, J = 2.5 Hz,
1 H), 1.33 (s, 6 H), 1.27 (s, 9 H). 13C NMR (125.8 MHz, CDCl3): δ = 169.6, 168.5, 80.9, 68.2, 32.9, 29.5, 27.4. IR (CH2Cl2): 3419, 2974, 1646, 1180, 1094 cm-1. HRMS: m/z calcd for C10H17NONa+: 190.1202; found: 190.1042. 26: solid; mp 108-110 °C. 1H NMR (500 MHz, CDCl3): δ = 8.23 (d, J = 9.0 Hz, 2 H), 7.93 (d, J = 9.0 Hz, 2 H), 5.57 (s, 1 H), 2.43 (s, 1 H), 1.78 (s, 6 H). 13C NMR (125.8 MHz, CDCl3): δ = 164.5, 149.4, 140.3, 128.1, 123.6, 86.4, 69.8, 49.3, 28.8. IR (CH2Cl2): 3289, 2982, 1654, 1527, 1352, 845 cm-1. HRMS: m/z calcd for C12H12N2O3Na+: 255.0740; found: 255.0738. 27: oil. 1H NMR (500 MHz, CDCl3): δ = 8.30 (d, J = 8.0 Hz, 2 H), 8.18 (d, J = 8.0 Hz, 2 H), 4.80 (d, J = 3.0 Hz, 1 H), 4.33 (d, J = 3.0 Hz, 1 H), 1.48 (s, 6 H). 13C NMR (125.8 MHz, CDCl3): δ = 167.2, 158.2, 149.6, 132.6, 129.1, 123.6, 83.5, 69.6, 29.5. IR (CH2Cl2): 3427, 3105, 2982, 1646, 1597, 1519, 1307, 1066 cm-1. HRMS: m/z calcd for C12H12N2O3Na+: 255.0740; found: 255.0739.