Biscarbene−Ruthenium Complexes in Catalysis
A R T I C L E S
128.1, 126.3, 125.6, 125.5, 122.9, 120.3, 31.4, 21.2. MS (EI): m/z
376.2392 (calc for C26H32O2 376.2402). FT-IR (KBr) ν (cm-1): 3050,
2964, 1758, 1608, 1367.
Ph). 13C NMR (50.329 MHz, CDCl3) δ ppm: 162.9, 147.6, 136.8, 135.9,
133.0, 129.5, 128.7, 128.6, 128.4, 128.2, 126.7, 122.4, 120.8, 64.3.
MS (EI): m/z 332.0386 (calc for C18H14O235Cl2 332.0371). FT-IR (KBr)
ν (cm-1): 3058, 3024, 1779, 1678, 1615, 1596.
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4. Yield: 85%. H NMR (200.131 MHz, CDCl3) δ ppm: 2.17 (s,
3H, Me), 3.77 (s, 3H, Me), 3.82 (s, 3H, Me), 6.15 (d, J ) 10.9 Hz,
1H, H1), 6.56 (d, J ) 15.6 Hz, 1H, H3), 6.80 (dd, J ) 10.9 Hz, J )
15.6 Hz, 1H, H2), 6.81 (dm, J ) 9.0 Hz, 2H, Ar), 6.91 (dm, J ) 9.0
Hz, 2H, Ar), 7.25 (dm, J ) 9.0 Hz, 2H, Ar), 7.39 (dm, J ) 9.0 Hz,
2H, Ar). 13C NMR (50.329 MHz, CDCl3) δ ppm: 169.7, 159.8, 159.3,
147.3, 133.3, 130.2, 129.7, 127.6, 127.2, 121.4, 119.6, 114.1, 113.9,
55.3, 55.3, 21.1. MS (EI): m/z 324.1367 (calc for C20H20O4 324.1361).
FT-IR (KBr) ν (cm-1): 3035, 3002, 1757, 1603, 1573. mp: 92 °C.
12. Yield: 70%. 19F NMR (188.31 MHz, CDCl3) δ ppm: -65.8.
1H NMR (200.131 MHz, CDCl3) δ ppm: 6.42 (d, J ) 11.2 Hz, 1H,
H1), 6.57 (m, 1H, H4), 6.74 (d, J ) 15.6 Hz, 1H, H3), 6.88 (m, 1H,
H5), 7.04 (dd, J ) 11.2 Hz, J ) 15.6 Hz, 1H, H2), 7.25-7.56 (m, 10H,
Ph). 13C NMR (50.329 MHz, CDCl3) δ ppm: 160.0, 147.6, 137.0, 135.4,
134.3, 133.8, 131.2, 129.3, 128.8, 128.7, 128.4, 128.0, 126.7, 122.8,
121.3, 121.0. MS (EI): m/z 344.1022 (calc for C20H15O2F3 344.1024).
FT-IR (KBr) ν (cm-1): 3062, 1750, 1683, 1598.
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1
5. Yield: 60%. H NMR (200.131 MHz, CDCl3) δ ppm: 2.19 (s,
13. Yield: 85%. H NMR (200.131 MHz, CDCl3) δ ppm: 3.55 (s,
3H, Me), 5.21 (d, J ) 11.0 Hz, 1H, dCH2), 5.30 (d, J ) 11.0 Hz, 1H,
dCH2), 5.71 (d, J ) 17.0 Hz, 1H, dCH2), 5.80 (d, J ) 16.6 Hz, 1H,
dCH2), 6.25 (d, J ) 11.2 Hz, 1H, H1), 6.63 (d, J ) 15.6 Hz, 1H, H3),
6.65-6.80 (m, 2H, dCH), 6.98 (dd, J ) 11.2 Hz, J ) 15.6 Hz, 1H,
H2), 7.30 (m, 4H, Ar), 7.40 (m, 4H, Ar). 13C NMR (50.329 MHz,
CDCl3) δ ppm: 169.6, 148.1, 138.1, 137.1, 136.8, 136.4, 136.3, 134.1,
134.0, 128.6, 126.7, 126.6, 126.4, 123.3, 120.6, 115.0, 113.9, 21.2.
2H, CH2CO), 6.35 (d, J ) 11.0 Hz, 1H, H1), 6.70 (d, J ) 15.6 Hz, 1H,
H3), 6.93 (dd, J ) 11.0 Hz, J ) 15.6 Hz, 1H, H2), 7.22-7.49 (m, 10H,
Ph). 13C NMR (50.329 MHz, CDCl3) δ ppm: 161.6, 147.7, 136.8, 135.8,
133.4, 129.4, 128.7, 128.7, 128.4, 128.1, 126.7, 122.4, 121.1, 112.7,
24.9. MS (EI): m/z 289.1112 (calc for C19H15O2N 289.1103). FT-IR
(KBr) ν (cm-1): 3058, 3040, 2261, 1766, 1636, 1595.
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14. Yield: 80%. H NMR (200.131 MHz, CDCl3) δ ppm: 1.52 (d,
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6. Yield: 91%. H NMR (200.131 MHz, CDCl3) δ ppm: 2.19 (s,
J ) 7.0 Hz, 3H, Me), 2.82 (d, J ) 5.0 Hz, 1H, OH), 4.44 (m, 1H,
CHOH), 6.29 (d, J ) 11.1 Hz, 1H, H1), 6.67 (d, J ) 15.6 Hz, 1H, H3),
6.95 (dd, J ) 11.1 Hz, J ) 15.6 Hz, 1H, H2), 7.20-7.37 (m, 10H, Ph).
13C NMR (50.329 MHz, CDCl3) δ ppm: 174.4, 147.8, 137.1, 135.1,
133.9, 129.2, 128.7, 128.6, 128.3, 127.9, 126.6, 122.8, 120.6, 66.9,
20.4. MS (EI): m/z 294.1256 (calc for C19H18O3 294.1256). FT-IR (KBr)
ν (cm-1): 3445, 3058, 3024, 1755, 1634, 1595.
3H, Me), 2.55 (s, 3H, ArCOCH3), 2.62 (s, 3H, ArCOCH3), 6.35 (d,
J ) 11.2 Hz, 1H, H1), 6.71 (d, J ) 15.6 Hz, 1H, H3), 7.02 (dd, J )
11.2 Hz, J ) 15.6 Hz, 1H, H2), 7.37 (d, J ) 8.5 Hz, 2H, Ar), 7.54 (d,
J ) 8.6 Hz, 2H, Ar), 7.85 (d, J ) 8.5 Hz, 2H, Ar), 7.98 (d, J ) 8.6
Hz, 2H, Ar). 13C NMR (50.329 MHz, CDCl3) δ ppm: 197.4, 169.3,
148.4, 141.4, 138.9, 137.2, 136.2, 134.2, 128.9, 128.6, 128.5, 126.6,
125.3, 121.6, 26.7, 26.6, 21.0. MS (EI): m/z 348.1365 (calc for C22H20O4
348.1361). FT-IR (KBr) ν (cm-1): 3053, 3002, 1758, 1681, 1637, 1598,
1560.
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15. Yield: 93%. H NMR (200.131 MHz, CDCl3) δ ppm: 3.47 (s,
3H, Me), 4.18 (s, 2H, CH2CO), 6.31 (d, J ) 11.1 Hz, 1H, H1), 6.66 (d,
J ) 15.6 Hz, 1H, H3), 6.95 (dd, J ) 11.1 Hz, 1H, J ) 15.6 Hz, H2),
7.22-7.47 (m, 10H, Ph). 13C NMR (50.329 MHz, CDCl3) δ ppm: 168.9,
147.7, 137.1, 134.8, 134.2, 129.1, 128.6, 128.5, 128.4, 127.8, 126.5,
123.1, 120.7, 69.8, 59.5. MS (EI): m/z 294.1262 (calc for C19H18O3
294.1256). FT-IR (KBr) ν (cm-1): 3058, 3024, 1772, 1684, 1636, 1595.
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7. Yield: 85%. H NMR (200.131 MHz, CD2Cl2) δ ppm: 2.22 (s,
3H, Me), 6.43 (d, J ) 11.1 Hz, 1H, H1), 6.76 (d, J ) 15.4 Hz, 1H,
H3), 6.98 (dd, J ) 11.1 Hz, J ) 15.4 Hz, 1H, H2), 7.44 (d, J ) 8.8 Hz,
2H, Ar), 7.62 (d, J ) 8.8 Hz, 2H, Ar), 8.15 (d, J ) 8.8 Hz, 2H, Ar),
8.29 (d, J ) 8.8 Hz, 2H, Ar). 13C NMR (50.329 MHz, CD2Cl2) δ ppm:
171.1, 150.1, 149.0, 145.0, 142.6, 135.7, 131.2, 129.1, 128.4, 126.0,
125.8, 124.0, 22.7. MS (EI): m/z 354.0867 (calc for C18H14O6N2
354.0852). FT-IR (KBr) ν (cm-1): 3055, 1758, 1653, 1589, 1507, 1340.
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16. Yield: 65%. H NMR (200.131 MHz, CDCl3) δ ppm: 6.31 (d,
J ) 11.0 Hz, 1H, H1), 6.69 (d, J ) 15.5 Hz, 1H, H3), 6.96 (dd, J )
11.0 Hz, J ) 15.5 Hz, 1H, H2), 7.23-7.47 (m, 10H, Ph), 8.20 (s, 1H,
CHO). 13C NMR (50.329 MHz, CDCl3) δ ppm: 159.6, 147.6, 136.9,
135.2, 133.3, 129.3, 128.7, 128.5, 128.4, 127.5, 126.3, 122.8, 120.4.
MS (EI): m/z 250.0987 (calc for C17H14O2 250.0994). FT-IR (KBr) ν
(cm-1): 3058, 3040, 2850, 1735, 1684, 1636, 1595.
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8. Yield: 81%. H NMR (200.131 MHz, CDCl3) δ ppm: 2.20 (s,
3H, Me), 6.36 (d, J ) 11.1 Hz, 1H, H1), 6.68 (d, J ) 15.6 Hz, 1H,
H3), 6.91 (dd, J ) 11.1 Hz, J ) 15.6 Hz, 1H, H2), 7.37 (dm, J ) 8.2
Hz, 2H, Ar), 7.54 (m, 4H, Ar), 7.70 (dm, J ) 8.6 Hz, 2H, Ar). 13C
NMR (50.329 MHz, CDCl3) δ ppm: 169.2, 148.0, 141.0, 138.7, 134.0,
132.5, 132.4, 129.0, 127.0, 125.6, 121.6, 118.8, 118.3, 112.8, 111.2,
21.0. MS (EI): m/z 314.1043 (calc for C20H14O2N2 314.1055). FT-IR
(KBr) ν (cm-1): 3054, 2226, 1760, 1634, 1599.
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17. Yield: 98%. H NMR (200.131 MHz, CDCl3) δ ppm: 6.44 (d,
J ) 11.2 Hz, 1H, H1), 6.71 (d, J ) 15.7 Hz, 1H, H3), 7.09 (dd, J )
11.2 Hz, J ) 15.7 Hz, 1H, H2), 7.22-7.62 (m, 13H, Ph), 8.14-8.19
(m, 2H, Ph). 13C NMR (50.329 MHz, CDCl3) δ ppm: 165.3, 148.5,
137.2, 134.6, 134.5, 133.6, 130.1, 129.6, 128.9, 128.7, 128.6, 128.5,
128.4, 127.8, 126.5, 123.3, 120.6. MS (EI): m/z 326.1343 (calc for
C23H18O2 326.1306). FT-IR (KBr) ν (cm-1): 3059, 3037, 1732, 1636,
1595.
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9. Yield: 85%. H NMR (200.131 MHz, CDCl3) δ ppm: 2.20 (s,
3H, Me), 6.34 (d, J ) 10.6 Hz, 1H, H1), 6.65 (d, J ) 15.6 Hz, 1H,
H3), 6.80 (dd, J ) 10.6 Hz, J ) 15.6 Hz, 1H, H2), 7.3-7.7 (m, 8H,
Ar). 13C NMR (50.329 MHz, CDCl3) δ ppm: 169.3, 147.3, 137.9, 135.7,
133.4, 132.9, 132.6, 131.8, 131.2, 130.6, 130.1, 129.6, 129.6, 124.4,
121.5, 118.6, 118.3, 113.2, 113.0, 21.0. MS (EI): m/z 314.1059 (calc
for C20H14O2N2 314.1055). Anal. Calcd for C20H14O2N2: C, 71.00; H,
4.31. Found: C, 70.75; H, 4.40. FT-IR (KBr) ν (cm-1): 3068, 2231,
1765, 1636, 1594, 1573.
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18. Yield: 45%. H NMR (200.131 MHz, CDCl3) δ ppm: 3.86 (s,
3H, Me), 6.39 (d, J ) 11.0 Hz, 1H, H1), 6.67 (d, J ) 15.6 Hz, 1H,
H3), 6.94 (dm, J ) 9.0 Hz, 2H, Ar), 7.05 (dd, J ) 11.0 Hz, J ) 15.6
Hz, 1H, H2), 7.22-7.40 (m, 8H, Ph), 7.52-7.57 (m, 2H, Ph), 8.09
(dm, J ) 9.0 Hz, 2H, Ar). 13C NMR (50.329 MHz, CDCl3) δ ppm:
165.1, 163.9, 148.6, 137.4, 134.8, 134.3, 132.2, 128.8, 128.6, 128.5,
128.4, 127.7, 126.5, 123.3, 121.9, 120.6, 113.8, 55.5. MS (EI): m/z
356.1407 (calc for C24H20O3 356.1412). FT-IR (KBr) ν (cm-1): 3045,
1727, 1636 (f, νCdC), 1605, 1580.
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10. Yield: 80%. H NMR (200.131 MHz, CDCl3) δ ppm: 2.21 (s,
3H, Me), 6.54 (d, J ) 11.1 Hz, 1H, H1), 6.74 (dd, J ) 11.1 Hz, J )
15.2 Hz, 1H, H2), 7.02 (d, J ) 15.2 Hz, 1H, H3), 7.25 (m, 1H, Ar),
7.4-7.8 (m, 7H, Ar). 13C NMR (50.329 MHz, CDCl3) δ ppm: 169.1,
146.9, 139.8, 137.6, 133.8, 133.3, 132.8, 132.7, 131.3, 131.1, 129.6,
128.1, 126.8, 125.8, 122.6, 117.8, 117.4, 112.1, 111.1, 20.8. MS (EI):
m/z 314.1043 (calc for C20H14O2N2 314.1055). FT-IR (KBr) ν (cm-1):
3057, 2227, 1757, 1636, 1593.
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19. Yield: 91%. H NMR (200.131 MHz, CDCl3) δ ppm: 2.02 (m,
3H, Me), 5.72 (m, 1H, H4), 6.31 (s, 1H, H5), 6.34 (d, J ) 11.2 Hz, 1H,
H1), 6.68 (d, J ) 15.6 Hz, 1H, H3), 7.04 (dd, J ) 11.2 Hz, J ) 15.6
Hz, 1H, H2), 7.24-7.54 (m, 10H, Ph). 13C NMR (50.329 MHz, CDCl3)
δ ppm: 166.1, 148.5, 137.2, 136.1, 134.7, 134.4, 128.9, 128.7, 128.5,
128.4, 127.7, 127.1, 126.5, 123.4, 120.5, 18.4. MS (EI): m/z 290.1304
(calc for C20H18O2 290.1307). FT-IR (KBr) ν (cm-1): 3082, 3058, 1733,
1636, 1595.
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11. Yield: 30%. H NMR (200.131 MHz, CDCl3) δ ppm: 6.07 (s,
1H, CHCl2), 6.40 (d, J ) 11.1 Hz, 1H, H1), 6.74 (d, J ) 15.6 Hz, 1H,
H3), 7.00 (dd, J ) 11.1 Hz, J ) 15.6 Hz, 1H, H2), 7.24-7.57 (m, 10H,
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J. AM. CHEM. SOC. VOL. 125, NO. 39, 2003 11973