J.-J. Cao et al. / Tetrahedron 70 (2014) 6985e6990
6989
JCeP¼2.7 Hz), 130.5 (s), 130.25 (s), 128.9 (d, JCeP¼17.3 Hz), 128.8 (s),
127.9 (d, JCeP¼12.2 Hz), 127.5 (d, JCeP¼41.7 Hz), 126.6 (s), 125.4 (d,
JCeP¼22.7 Hz), 123.9 (d, JCeP¼2.6 Hz), 122.5 (s), 119.6 (d,
cmꢁ1) 1630, 1503, 1451, 1183, 835, 769, 717; HRMS calcd for
C
25H18FNOPþ (CIþ, MþHþ): 398.1110; found: 398.1111.
JCeP¼1.6 Hz). 31P NMR (243 MHz, CDCl3) (
d
, ppm): 33.58; IR (neat,
n
,
4.2.13. 2-Chloro-6-(diphenylphosphoryl)phenanthridine (3m). Yield
118 mg, 57%. White solid. Mp 243e244 ꢀC; 1H NMR (600 MHz,
cmꢁ1)1437, 1192, 1108, 760, 699; HRMS calcd for C29H21NOPþ (CIþ,
MþHþ): 430.1361; found: 430.1361.
CDCl3) (
d
, ppm): 9.41 (d, J¼8.3 Hz, 1H), 8.52e8.43 (m, 2H), 7.90 (d,
J¼8.7 Hz,1H), 7.86e7.80 (m, 4H), 7.80e7.76 (m,1H), 7.64 (dd, J¼11.3,
4.0 Hz, 1H), 7.56 (dd, J¼8.7, 2.1 Hz, 1H), 7.48e7.42 (m, 2H), 7.38 (td,
4.2.9. 9-(Diphenylphosphoryl)dibenzo[i,k]phenanthridine (3i). Yield
117 mg, 49%. Yellow solid. Mp 266e269 ꢀC; 1H NMR (600 MHz,
J¼7.6, 3.0 Hz, 4H); 13C NMR (151 MHz, CDCl3) (
d, ppm): 157.2 (d,
CDCl3) (
d
, ppm): 8.75 (d, J¼8.1 Hz,1H), 8.65 (t, J¼8.8 Hz, 2H), 8.58 (d,
JCeP¼127.6 Hz), 141.1 (d, JCeP¼23.4 Hz), 134.9 (s), 132.9 (s), 132.6 (s),
132.3 (d, JCeP¼9.3 Hz), 131.8 (d, JCeP¼2.7 Hz), 131.6 (d, JCeP¼6.7 Hz),
131.3 (s), 129.3 (s), 128.6 (d, JCeP¼14.9 Hz), 128.2 (d, JCeP¼12.2 Hz),
127.9 (d, JCeP¼22.9 Hz), 125.4 (d, JCeP¼2.3 Hz), 122.2 (s), 121.8 (s).
J¼8.0 Hz, 1H), 8.42 (d, J¼8.1 Hz, 1H), 8.05 (d, J¼8.1 Hz, 1H),
7.92e7.83 (m, 4H), 7.72e7.67 (m, 1H), 7.65e7.61 (m, 1H), 7.59 (tdd,
J¼7.1, 2.7, 1.2 Hz, 2H), 7.54e7.48 (m, 1H), 7.41e7.34 (m, 3H), 7.30 (td,
J¼7.6, 3.0 Hz, 4H); 13C NMR (151 MHz, CDCl3) (
d
, ppm): 153.4 (d,
31P NMR (243 MHz, CDCl3) ( , cmꢁ1)1583,
d, ppm): 28.51; IR (neat, n
JCeP¼128.6 Hz),144.8 (d, JCeP¼23.1 Hz),134.5 (d, JCeP¼6.5 Hz), 134.4
(s), 133.3 (d, JCeP¼116.8 Hz), 132.2 (d, JCeP¼8.8 Hz), 131.3 (s), 130.0
(s), 129.6 (d, JCeP¼32.3 Hz), 128.8 (d, JCeP¼68.4 Hz), 128.1 (s), 128.0
(d, JCeP¼12.1 Hz), 128.0 (s), 127.8 (d, JCeP¼23.1 Hz), 127.3 (s), 126.7
(d, JCeP¼64.6 Hz), 126.0 (d, JCeP¼21.3 Hz), 124.0 (s), 123.2 (s), 122.5
1489, 1432, 1207, 1112, 774, 703; HRMS calcd for C25H17ClNOP (CIþ,
M): 413.0736; found: 413.0730.
4.2.14. 6-(Diphenylphosphoryl)-2-nitrophenanthridine (3n). Yield
64 mg, 30%. Yellow solid. Mp 225e227 ꢀC; 1H NMR (400 MHz,
(s). 31P NMR (243 MHz, CDCl3) (
d
, ppm): 28.58; IR (neat,
n
, cmꢁ1
)
CDCl3) (
d
, ppm): 9.41 (d, J¼8.3 Hz, 1H), 9.20 (d, J¼8.3 Hz, 1H), 8.97
1437, 1178, 1117, 732, 755, 699; HRMS calcd for C33H23NOPþ (CIþ,
(dd, J¼4.2, 1.3 Hz, 1H), 8.25 (dd, J¼8.2, 1.3 Hz, 1H), 7.93e7.78 (m,
5H), 7.78e7.68 (m, 1H), 7.58 (dd, J¼8.3, 4.3 Hz, 1H), 7.46 (td, J¼7.3,
1.2 Hz, 2H), 7.38 (ddd, J¼7.2, 5.4, 2.4 Hz, 4H); 13C NMR (101 MHz,
MþHþ): 480.1517; found: 480.1512.
4.2.10. 6-(Diphenylphosphoryl)-2-methylphenanthridine (3j). Yield
138 mg, 70%. White solid. Mp 222e223 ꢀC; 1H NMR (400 MHz,
CDCl3) (
d
, ppm): 158.5 (d, JCeP¼125.7 Hz),151.1 (s),141.0 (s),138.2 (s,
3H), 137.6 (d, JCeP¼23.6 Hz), 133.5 (d, JCeP¼7.4 Hz), 133.1 (s), 132.3
(d, JCeP¼9.3 Hz), 132.0 (s), 131.9 (d, JCeP¼2.7 Hz), 131.6 (s), 123.0 (d,
JCeP¼23.2 Hz), 129.6 (s), 128.3 (d, JCeP¼12.2 Hz), 128.0 (s), 123.9 (s),
CDCl3) (
d
, ppm): 9.39 (d, J¼8.3 Hz, 1H), 8.56 (d, J¼8.3 Hz, 1H), 8.29
(s, 1H), 7.85 (dd, J¼12.0, 7.5 Hz, 5H), 7.74 (t, J¼7.7 Hz, 1H), 7.59 (t,
J¼7.7 Hz,1H), 7.50e7.40 (m, 3H), 7.40e7.32 (m, 4H), 2.55 (s, 3H); 13
C
123.7 (s). 31P NMR (162 MHz, CDCl3) (
d, ppm): 28.63; IR (neat, n,
NMR (101 MHz, CDCl3) (
d, ppm): 155.6 (d, JCeP¼129.5 Hz), 141.2 (d,
cmꢁ1
)
1700, 1510, 1342, 1199, 702; HRMS calcd for
JCeP¼23.4 Hz), 139.1 (s), 133.1 (d, JCeP¼104.6 Hz), 132.3 (d,
JCeP¼9.2 Hz), 131.6 (d, JCeP¼2.8 Hz), 130.9 (d, JCeP¼1.0 Hz), 130.8 (s),
130.56 (s),128.5 (s),128.2 (d, JCeP¼12.2 Hz),127.9 (s),127.8 (s), 124.2
(d, JCeP¼2.5 Hz), 122.1 (d, JCeP¼1.5 Hz), 121.7 (d, JCeP¼0.7 Hz), 22.2
C
25H18N2O3Pþ (CIþ, MþHþ): 425.1055; found: 425.1011.
4.2.15. Ethyl phenanthridin-6-yl(phenyl)phosphinate (4a). Yield
139 mg, 80%. Yellow oil. 1H NMR (600 MHz, CDCl3) (
, ppm): 9.21 (d,
d
(s). 31P NMR (162 MHz, CDCl3) (
d, ppm): 28.26; IR (neat,
n
, cmꢁ1
)
J¼8.3 Hz, 1H), 8.51 (d, J¼8.2 Hz, 1H), 8.45 (d, J¼7.6 Hz, 1H), 8.09 (d,
J¼7.4 Hz, 1H), 7.96 (t, J¼9.7 Hz, 2H), 7.76e7.65 (m, 2H), 7.61 (t,
J¼7.3 Hz, 3H), 7.35 (d, J¼2.3 Hz, 2H), 4.55e4.15 (m, 2H), 1.38 (t,
3058, 1611, 1484, 1442, 1202, 1113, 764, 703; HRMS calcd for
C
26H21NOPþ (CIþ, MþHþ): 394.1361; found: 394.1360.
J¼7.0 Hz, 3H); 13C NMR (151 MHz, CDCl3) (
d, ppm): 155.7 (d,
4.2.11. 6-(Diphenylphosphoryl)-3-methoxyphenanthridine
JCeP¼161.5 Hz), 143.0 (d, JCeP¼24.0 Hz), 133.1 (d, JCeP¼2.9 Hz), 132.6
(d, JCeP¼8.2 Hz), 132.4 (d, JCeP¼9.9 Hz), 132.3 (d, JCeP¼2.8 Hz), 131.2
(d, JCeP¼0.8 Hz),130.9 (s),130.9 (d, JCeP¼9.9 Hz),130.32 (s),128.8 (d,
JCeP¼5.1 Hz), 128.7 (d, JCeP¼2.5 Hz),128.3 (d, JCeP¼3.9 Hz),128.2 (s),
127.8 (s), 126.9 (d, JCeP¼26.9 Hz), 124.5 (d, JCeP¼2.8 Hz), 122.1 (d,
JCeP¼1.7 Hz), 122.0 (s), 62.4 (d, JCeP¼6.6 Hz), 16.6 (d, JCeP¼6.6 Hz).
(3k). Yield 133 mg, 65%. White solid. Mp 182e184 ꢀC; 1H NMR
(400 MHz, CDCl3) (
d
, ppm): 9.40 (d, J¼8.4 Hz, 1H), 8.48 (d, J¼8.4 Hz,
1H), 8.41 (d, J¼9.0 Hz, 1H), 7.85 (dd, J¼11.7, 7.3 Hz, 4H), 7.73 (t,
J¼7.6 Hz, 1H), 7.54 (t, J¼7.6 Hz, 1H), 7.45 (t, J¼7.2 Hz, 2H), 7.38 (td,
J¼7.4, 2.7 Hz, 4H), 7.35e7.25 (m, 2H), 3.87 (s, 3H); 13C NMR
(101 MHz, CDCl3) (
d
, ppm): 160.1 (s), 157.1 (d, JCeP¼128.5 Hz), 144.4
31P NMR (243 MHz, CDCl3) ( , cmꢁ1) 2994,
d, ppm): 28.65; IR (neat, n
(d, JCeP¼23.5 Hz), 133.6 (s), 132.9 (s), 132.51 (s), 132.3 (d,
JCeP¼9.3 Hz), 131.7 (d, JCeP¼2.7 Hz), 131.1 (s), 128.6 (s), 128.2 (d,
JCeP¼12.2 Hz), 127.2 (d, JCeP¼23.1 Hz), 126.8 (s), 123.3 (s), 121.6 (s),
120.1 (s), 118.6 (d, JCeP¼2.4 Hz), 110.6 (s), 55.7 (s). 31P NMR
1451, 1216, 1042, 920; HRMS calcd for C21H19NO2Pþ (CIþ, MþHþ):
348.1153; found: 348.1165.
4.2.16. Diethyl phenanthridin-6-ylphosphonate (4b). Yield 50 mg,
(162 MHz, CDCl3) (
d
, ppm): 28.46; IR (neat,
n
, cmꢁ1) 3060, 3000,
32%. Yellow oil. 1H NMR (600 MHz, CDCl3) (
d, ppm): 8.96 (d,
2951, 1621, 1475, 1442, 1183, 844, 750, 703; HRMS calcd for
C
J¼8.3 Hz, 1H), 8.68 (d, J¼8.3 Hz, 1H), 8.61 (d, J¼8.2 Hz, 1H), 8.30 (d,
26H21NO2Pþ (CIþ, MþHþ): 410.1310; found: 410.1316.
J¼7.4 Hz, 1H), 7.89 (t, J¼7.6 Hz, 1H), 7.81e7.72 (m, 3H), 4.48e4.34
(m, 4H), 1.43 (t, J¼7.0 Hz, 6H, CH3); 13C NMR (151 MHz, CDCl3) (
d,
4.2.12. 6-(Diphenylphosphoryl)-2-fluorophenanthridine (3l). Yield
111 mg, 56%. White solid. Mp 235e237 ꢀC; 1H NMR (600 MHz,
ppm): 174.9 (s, 1H), 162.7 (s), 153.5 (d, JCeP¼221.5 Hz), 143.0 (d,
JCeP¼27.2 Hz), 138.8 (s), 137.0 (s), 132.6 (d, JCeP¼9.8 Hz), 131.3 (s),
131.0 (s), 130.5 (s), 129.5 (s), 128.9 (d, JCeP¼2.4 Hz), 128.8 (s), 128.5
(s), 128.3 (d, JCeP¼8.6 Hz), 128.1 (s), 127.8 (d, JCeP¼6.7 Hz), 126.2 (d,
JCeP¼30.0 Hz), 124.7 (d, JCeP¼3.4 Hz), 122.2 (d, JCeP¼2.3 Hz), 122.0
(d, JCeP¼0.9 Hz), 63.6 (d, JCeP¼6.4 Hz), 58.4 (s). 31P NMR (243 MHz,
CDCl3) (
d
, ppm): 9.41 (d, J¼8.3 Hz, 1H), 8.44 (d, J¼8.2 Hz, 1H), 8.10
(dd, J¼9.9, 1.9 Hz, 1H), 7.96 (dd, J¼8.8, 5.8 Hz, 1H), 7.83 (dd, J¼11.4,
7.9 Hz, 4H), 7.78 (t, J¼7.6 Hz, 1H), 7.64 (t, J¼7.6 Hz, 1H), 7.45 (t,
J¼7.2 Hz, 2H), 7.37 (dt, J¼10.2, 3.9 Hz, 6H); 13C NMR (151 MHz,
CDCl3) (
d
, ppm): 162.4 (d, JCeF¼250.0 Hz), 156.5 (d, JCeP¼3.0 Hz),
CDCl3) (d, ppm): 10.05; IR (neat, n
, cmꢁ1) 2983, 1440, 1381, 1249,
155.6 (d, JCeP¼2.9 Hz), 139.6 (d, JCeP¼22.1 Hz), 133.6 (d,
JCeP¼1.1 Hz), 133.5 (d, JCeP¼1.1 Hz), 133.0 (s), 132.3 (s), 132.3 (d,
JCeP¼9.3 Hz), 132.0 (d, JCeP¼4.3 Hz), 132.0 (d, JCeP¼4.4 Hz), 131.8 (d,
JCeP¼2.8 Hz), 131.1 (s), 128.6 (d, JCeP¼13.7 Hz), 128.2 (d,
JCeP¼12.2 Hz), 127.7 (d, JCeP¼23.1 Hz), 126.0 (dd, JCeP¼9.6, 2.4 Hz),
122.3 (s), 117.8 (d, JCeP¼24.5 Hz), 107.2 (d, JCeP¼1.2 Hz), 107.0 (d,
1047, 910, 736; HRMS calcd for
316.1103; found: 316.1097.
C
17H19NO3Pþ (CIþ, MþHþ):
4.2.17. Dimethyl phenanthridin-6-ylphosphonate (4c). Yield 47 mg,
33%. Yellow oil. 1H NMR (400 MHz, CDCl3) (
, ppm): 9.52 (d,
d
J¼8.3 Hz,1H, ArH), 9.30 (d, J¼8.3 Hz,1H), 9.07 (dd, J¼4.3,1.6 Hz,1H),
JCeP¼1.0 Hz). 31P NMR (243 MHz, CDCl3) (
d, ppm): 28.53; IR (neat, n,
8.35 (dd, J¼8.3, 1.6 Hz, 1H), 7.95 (ddd, J¼11.8, 9.1, 1.2 Hz, 5H),