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cyclized product was subjected to oxidation by overnight reflux in
nitrobenzene solvent. In the final step, a Suzuki cross-coupling re-
action was performed with the oxidized product to achieve 7.
151.0, 146.3, 145.7, 134.0, 132.6, 131.7, 131.0, 127.8, 127.7, 127.0,
126.5, 125.7, 123.5, 122.2, 121.2, 120.4, 120.2, 118.9, 34.9, 30.9 ppm;
HRMS (EI): m/z calcd for C24H20N2O: 352.1576; found: 352.1567;
FTIR: v˜ =1680, 1596, 1551, 768 cmÀ1
.
2-methoxy-14H-quinazolino[3,2-f]phenanthridin-14-one
(5d):
1
White solid (88%); m.p. 174–1768C; H NMR (600 MHz, CDCl3) d=
8.96 (d, J=12 Hz, 1H), 8.79 (d, J=6 Hz, 1H), 8.42 (d, J=6 Hz, 1H),
8.12 (d, J=6 Hz, 1H), 8.09 (d, J=12 Hz, 1H),7.84 À7.82 (m, 2H),
7.67 (t, J=6 Hz, 1H) 7.53–7.50 (m, 2H), 7.07–7.05 (m, 1H),
3.95 ppm (s, 3H); 13C NMR (150 MHz, CDCl3) d=162.8, 158.8, 146.3,
145.6, 134.1, 133.9, 131.7, 131.1, 127.8, 127.0, 126.9, 126.5, 125.7,
125.6, 123.6, 120.7, 120.2, 115.9, 114.0, 105.9, 55.2 ppm; HRMS (EI):
m/z calcd for C21H14N2O2: 326.1055; found: 326.1064; FTIR: v˜ =
1677,1610, 1557, 759 cmÀ1
.
2-fluoro-14H-quinazolino[3,2-f]phenanthridin-14-one (5e): White
solid (53%); m.p. 213–2158C; 1H NMR (600 MHz, CDCl3) d=9.06–
9.03 (m, 1H), 9.01 (d, J=12 Hz, 1H), 8.43 (d, J=6 Hz, 1H), 8.25–
8.23 (m, 1H), 8.15 (d, J=6 Hz, 1H), 7.86 À7.83 (m, 2H), 7.73 (t, J=
6 Hz, 1H), 7.60 (t, J=6 Hz, 1H), 7.55–7.53 (m, 1H), 7.26–7.23 ppm
(m, 1H); 13C NMR (150 MHz, CDCl3) d=162.5, 162.2, 160.5, 145.8,
145.5, 134.4, 133.8, 133.7, 131.9, 130.3, 128.0, 127.0, 126.6, 126.2,
126.0, 124.2, 121.2, 120.1, 119.0, 113.8, 113.7, 109.3, 109.1 ppm (ad-
ditional peaks appeared due to the splitting by the fluoro group);
HRMS (EI): m/z calcd for C20H11FN2O: 314.0833; found: 314.0855;
Typical procedure for a Pd-Catalyzed intramolecular CÀH amina-
tion: To a solution of 4 or 7 (59.6 mg, 0.2 mmol, 1.0 equiv) in DMF
(3 mL), Pd(OAc)2 (1.8 mg, 0.01 mmol, 5 mol%) and Cu(OAc)2
(80 mg, 0.4 mmol, 2 equiv) were added in a sealed tube (50 mL)
under oxygen atmosphere. The reaction mixture was stirred for
15 min at room temperature and then heated at 1608C while vigo-
rously stirring for 48 h. The reaction mixture was then cooled to
room temperature, diluted with dichloromethane, and filtered
through a small pad of celite. The filtrate was concentrated in
vacuo and purified by either silica gel or neutral alumina packed
flash column chromatography with petroleum ether/ethyl acetate
(24:1) as the eluent to afford the desired product 5 or 8.
FTIR: v˜ =1682, 1604, 1556, 757 cmÀ1
.
2-chloro-14H-quinazolino[3,2-f]phenanthridin-14-one (5f): White
1
solid (71%); m.p. 199–2018C; H NMR (600 MHz, CDCl3) d=9.24 (s,
1H), 8.98 (d, J=6 Hz, 1H), 8.42 (d, J=6 Hz, 1H), 8.15 (t, J=6 Hz,
2H), 7.86–7.82 (m, 2H), 7.72 (t, J=6 Hz, 1H), 7.61 (t, J=6 Hz, 1H),
7.55–7.53 (m, 1H), 7.46 ppm (d, J=12 Hz, 1H); 13C NMR (150 MHz,
CDCl3) d= 62.4, 145.5, 145.5, 134.4, 133.6, 133.3, 131.9, 130.0,
128.4, 127.9, 127.0, 126.6, 126.3, 126.1, 123.7, 121.8, 121.3, 121.2,
120.2 ppm; HRMS (EI): m/z calcd for C20H11ClN2O: 330.0560; found:
330.0562; FTIR: v˜ =1689, 1599, 1554, 759 cmÀ1
.
2-bromo-14H-quinazolino[3,2-f]phenanthridin-14-one (5g): Gray-
1
ish White solid (73%); m.p. 180–1828C; H NMR (600 MHz, CDCl3)
d=9.35 (s, 1H), 8.92 (d, J=6 Hz, 1H), 8.40 (d, J=12 Hz, 1H), 8.09
(d, J=6 Hz, 1H), 8.03 (d, J=6 Hz, 1H), 7.82–7.78 (m, 2H), 7.67 (t,
J=6 Hz, 1H), 7.58–7.51 ppm (m, 3H); 13C NMR (150 MHz, CDCl3)
d=162.3, 145.4, 134.3, 133.3, 131.8, 130.0, 129.1, 128.4, 127.8,
127.0, 126.6, 126.3, 126.1, 124.6, 123.8, 123.6, 121.6, 121.5, 121.2,
120.1 ppm; HRMS (EI): m/z calcd for C20H11BrN2O: 374.0055; found:
14H-quinazolino[3,2-f]phenanthridin-14-one (5a): White solid
(79%); m.p. 167–169; 1H NMR (600 MHz, CDCl3) d=9.10 (d, J=
12 Hz, 1H), 8.99 (d, J=6 Hz, 1H), 8.43 (d, J=12 Hz, 1H), 8.23 (dd,
J1 =6 Hz, J2 =12 Hz, 2H), 7.82 (d, J=6 Hz, 2H), 7.72 (t, J=6 Hz, 1H),
7.59 (t, J=6 Hz, 1H), 7.53–7.47 ppm (m, 3H), 13C NMR (150 MHz,
CDCl3) d=162.5, 146.0, 145.7, 134.1, 132.6, 131.7, 130.9, 128.1,
127.8, 127.7, 126.9, 126.7, 126.5, 126.0, 125.8, 122.6, 121.7, 121.4,
120.4 ppm; HRMS (EI): m/z calcd for C20H12N2O: 296.0950; found:
374.0043; FTIR: v˜ =1684, 1595, 1549, 759 cmÀ1
.
2-phenyl-14H-quinazolino[3,2-f]phenanthridin-14-one
(5h):
1
296.0955; FTIR: v˜ =1687, 1602, 1554, 748 cmÀ1
.
White solid (68%); m.p. 179–1818C; H NMR (600 MHz, CDCl3) d=
9.41 (s, 1H), 9.02 (d, J=12 Hz, 1H), 8.45 (d, J=6 Hz, 1H), 8.29 (d,
J=12 Hz, 1H), 8.23 (d, J=12 Hz, 1H), 7.85–7.83 (m, 2H), 7.77–7.72
(m, 4H), 7.62–7.59 (m, 1H), 7.54–7.49 (m, 3H), 7.43–7.40 ppm (m,
1H); 13C NMR (150 MHz, CDCl3) d=162.7, 146.1, 145.7, 140.4, 139.7,
134.1, 133.0, 131.8, 130.7, 128.5, 128.0, 127.8, 127.4, 127.0, 126.9,
126.7, 126.5, 125.8, 124.7, 123.0, 121.6, 121.4, 120.37, 120.36 ppm;
HRMS (EI): m/z calcd for C26H16N2O: 372.1263, found: 372.1262;
2-methyl-14H-quinazolino[3,2-f]phenanthridin-14-one
(5b):
1
White solid (82%); m.p. 146–1488C; H NMR (600 MHz, CDCl3) d=
8.97 (d, J=12 Hz, 1H), 8.91 (s, 1H), 8.43–8.41 (m, 1H), 8.15 (d, J=
6 Hz, 1H), 8.10 (d, J=6 Hz, 1H), 7.82 À7.81 (m, 2H), 7.70–7.68 (m,
1H), 7.57–7.50 (m, 2H), 7.28 (d, J=6 Hz, 1H), 2.51 ppm (s, 3H);
13C NMR (150 MHz, CDCl3) d=162.6, 146.1, 145.7, 137.9, 134.0,
132.5, 131.7, 131.0, 127.7, 127.6, 127.1, 127.0, 126.5, 126.3, 125.7,
122.5, 121.9, 121.1, 120.4, 120.1, 21.5 ppm; HRMS (EI): m/z calcd for
C21H14N2O: 310.1106; found: 310.1073; FTIR: v˜ =1686, 1597, 1548,
FTIR: v˜ =1678, 1590, 1552, 760 cmÀ1
.
7-fluoro-14H-quinazolino[3,2-f]phenanthridin-14-one (5i): White
1
solid (78%); m.p. 210–2128C; H NMR (600 MHz, CDCl3) d=9.12 (d,
766 cmÀ1
.
J=12 Hz, 1H), 8.68 (d, J=6 Hz, 1H), 8.44 (d, J=12 Hz, 1H), 8.24–
8.19 (m, 2H), 7.84 (s, 2H), 7.56–7.44 ppm (m, 4H); 13C NMR
(150 MHz, CDCl3) d=163.0, 162.4, 161.3, 145.4, 145.0, 134.2, 132.3,
128.9, 128.9, 127.6, 127.4, 127.0, 126.6, 126.2, 123.9, 123.8, 122.5,
122.0, 121.8, 120.5, 120.0, 119.8, 113.5, 113.4 ppm (additional peaks
appeared due to the splitting by the fluoro group); HRMS (EI): m/z
2-tert-butyl-14H-quinazolino[3,2-f]phenanthridin-14-one
(5c):
1
White solid (81%); m.p. 152–1548C; H NMR (600 MHz, CDCl3) d=
9.22 (s, 1H), 9.02 (d, J=12 Hz, 1H), 8.47 (d, J=6 Hz, 1H), 8.23–8.20
(m, 2H), 7.86–7.82 (m, 2H), 7.74–7.72 (m, 1H), 7.59 (t, 1H), 7.56–
7.52 (m, 2H), 1.46 ppm (s, 9H); 13C NMR (150 MHz, CDCl3) d=162.7,
Chem. Eur. J. 2016, 22, 3506 – 3512
3510
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