7258 J . Org. Chem., Vol. 62, No. 21, 1997
Bouaucheau et al.
4-Ben zyl-4-ph en yl-1,2,3,4,7,11b-h exah ydr opyr r olo(3,2,1-
d e)p h en a n th r id in -2-on e (61) a n d 11c-Ben zyl-4-p h en yl-
1,2,3,7,11b,11c-h exah ydr opyr r olo(3,2,1-de)ph en an th r idin -
5-on e (62). Thermolysis of complex 58 (0.150 g, 0.270 mmol)
in refluxing benzene (10 mL) for 2.5 h led to two compounds,
which were separated by silica gel chromatography. Elution
with petroleum ether:ethyl acetate (90:10) gave 61 as a solid
(0.045 g, 43%): mp 64 °C; IR (CHCl3, cm-1) 1700; 1H NMR
(400 MHz, CDCl3) δ 7.43-7.04 (m, 14 H, Ar), 4.79 (d, 1 H, J )
16 Hz, CHPh), 3.90 (d, 1 H, J ) 16 Hz, CHPh), 3.66 (d, 1 H,
J ) 12.5 Hz, H-7), 3.30 (d, 1 H, J ) 12.5, H-7), 3.11 (m, 1 H,
H-11b), 2.57 (m, 1 H, H-1), 2.36-2.03 (m, 3 H, 2 H-3, H-2),
1.75-1.63 (m, 2 H, H-1, H-2); 13C NMR (50 MHz, CDCl3) δ
178.66 (CO), 136.48 (C-11c), 132.15-124.75 (Ar), 114.41 (C-
3a), 62.38 (C-4), 41.45 (CHPh), 40.48 (C-7), 32.67 (C-11b), 26.78
(C-1), 22.26 (C-2), 21.02 (C-3). HRMS calcd for C28H25NO
(M+): 391.1936. Found: 391.1934. Elution with the same
solvents (80:20) gave 62 (0.020 g, 19%) as a solid: mp 170 °C;
separated by silica gel chromatography. Elution with petro-
leum ether:ethyl acetate 85:25 gave 69 ( 0.040 g, 17%) as a
solid: mp 40-42 °C; IR (CHCl3, cm-1) 1650; 1H NMR (400
MHz, CDCl3) δ 7.39-7.06 (m, 5 H, Ar), 6.68 (s, 1 H), 6.66 (s,
1 H) (H-8, H-11), 5.93 (s, 2 H, OCH2O), 4.89 (d, 1 H, J ) 15.8
Hz, CHPh), 3.97 (d, 1 H, J ) 15.8 Hz, CHPh), 3.17 (d, 1 H, J
) 13.7 Hz, H-7), 3.09 (m, 1 H, H-11b), 3.01 (d, 1 H, J ) 13.7
Hz, H-7), 2.80 (m, 1 H, H-3), 2.55 (m, 1 H, H-3), 2.10 (m, 1 H,
H-2), 1.93 (m, 1 H, H-1), 1.73 (m, 2 H, H-2, H-1), 0.09 (s, 9 H,
SiMe3); 13C NMR (50 MHz, CDCl3) δ 175.71 (CO), 174.46 (C-
3a), 146.63, 145.95 (C-9, C-10), 135.27 (C-4), 132.34-126.79
(C-11a, C-7a, Ar), 107.26, 106.57 (C-8, C-11), 100.91 (OCO),
68.26 (C-11c), 44.76 (C-11b), 42.69 (C-7), 40.69 (CHPh), 26.22
(C-1), 24.98 (C-3), 0.98 (SiMe3). HRMS cald for C20H29NO3Si
(M+): 431.1923. Found: 431.1922. Elution with the same
sovents (70:30) gave 70 (0.029 g, 10%) as a solid: mp 54-56
°C; IR (CHCl3, cm-1) 1665; 1H NMR (400 MHz, CDCl3) δ 7.29-
7.19 (m, 5 H, Ar), 6.75 (s, 1 H), 6.71 (s, 1 H (H-8, H-11), 5.96
(s, 2 H, OCH2O), 4.85 (d, 1 H, J ) 10.8 Hz, CHPh), 4.46 (d, 1
H, J ) 16.8 Hz, CHPh), 3.68 (dd, 2 H, J ) 12.2 and 14.8 Hz,
2 H-7), 3.32 (d, 1 H, J ) 10.7 Hz, H-11c), 2.79 (m, 1 H, H-3),
2.38 (m, 1 H, H-1), 2.20-2.17 (m, 3 H, H-3, H-2, H-11b), 1.47
(m, 2 H, H-1, H-2); 13C NMR (50 MHz, CDCl3) δ 171.76 (CO),
153.80 (C-3a), 147.20, 146.61 (C-9, C-10), 139.69 (C-4), 128.69-
126.20 (C-11a, C-7a, Ar), 107.60, 104.63 (C-8, C-11), 101.25
(OCO), 62.28 (C-11c), 45.42 (C-11b), 43.39 (CHPh), 29.69 (C-
7), 27.08 (C-2), 25.83 (C-1), 25.36 (C-13). HRMS calcd for
1
IR (CHCl3, cm-1) 1670; H NMR (400 MHz, CDCl3) δ 7.41-
7.15 (m, 14 H, Ar), 5.14 (d, 1 H, J ) 16.1 Hz, CHPh), 4.14 (d,
1 H, J ) 16.1 Hz, CHPh), 3.34 (d, 1 H, J ) 13.7 Hz, H-7), 3.31
(m, 1 H, H-11b), 3.19 (d, 1 H, J ) 13.6 Hz, H-7), 2.95-2.91
(m, 1 H, H-3), 2.63-2.59 (m, 1 H, H-3), 2.14 -2.08 (m, 2 H,
H-1, H-2 ), 1.96 (m, 1 H, H-1), 1.79 (m, 1 H, H-2); 13C NMR
(50 MHz, CDCl3) δ 172.10 (CO), 159.87 (C-3a), 135.25 (C-4),
132.48-126.45 (Ar), 66.02 (C-11c), 44.57 (C-11b), 43.42 (C-7),
41.49 (CHPh), 25.80 (C-1), 24.31 (C-2), 23.49 (C-3). HRMS
calcd for C21H18NO (M+): 300.1388. Found: 300.1388.
4-Ben zyl-9,10-m et h ylen ed ioxo-4-p h en yl-1,2,3,4,7,11b -
h exah ydr opyr r olo(3,2,1-de)ph en an th r idin -5-on e (67) an d
11c-Ben zyl-9,10-(m et h ylen ed ioxo)-4-p h en yl-1,2,3,7,11b -
h exa h yd r op yr r olo(3,2,1-d e)p h en a n t h r id in -5-on e (68).
Thermolysis of complex 66a (0.23 g, 0.387 mmol) in refluxing
benzene (20 mL) for 5.5 h led to two compounds, which were
separated by silica gel chromatography. Elution with petro-
leum ether:ethyl acetate 85:15 gave 67 (0.075 g, 44.5%) as a
solid: mp 102 °C; IR (CHCl3, cm-1) 1700; 1H NMR (400 MHz,
CDCl3) δ 7.41-7.01 (m, 10 H, Ar), 6.74 (s, 1 H), 6.59 (s, 1 H,
H-8, H-11), 5.96 (s, 2 H, OCH2O), 4.66 (d, 1 H, J ) 15.8 Hz,
CHPh), 3.79 (d, 1 H, J ) 15.7, CHPh), 3.65 (d, 1 H, J ) 12.6,
H-7), 3.28 (d, 1 H, J ) 12.5 Hz, C-7), 3.03 (m, 1 H, H-11a),
2.46 (m, 1 H, H-1), 2.24 (m, 1 H, H-3), 2.09-2.05 (m, 2 H, H-2,
H-3), 1.68 (m, 1 H, H-2), 1.58 (m, 1 H, H-1); 13C NMR (100
MHz, CDCl3) δ 178.47 (CO), 147.23, 146.04 (C-9, C-10), 138.90
(C-11c), 137.25-125.40 (C-7a, C-11a, Ar), 114.24 (C-3a),
107.23, 105.39 (C-8, C-11), 101.18 (OCO), 62.38 (C-4), 41.37
(CHPh), 40.37 (C-7); 32.49 (C-11b), 27.22 (C-1), 22.20 (C-2),
20.99 (C-3). HRMS calcd for C29H25NO3 (M+): 435.1834;
Found: 435.1834. Elution with the same solvents (80:20) gave
C
23H21NO3 (M+): 359.1521. Found: 359.1520.
1-(5′-P h en ylp en t-4′-yn yl)p ip er id in -2-on e (71, n ) 4).
Alkylation of piperidin-2-one (3.96 g, 40 mmol) as above with
the related triflate (13.1 g, 45 mmol) in the presence of NaH
(2 g, 50 mmol) led after silica gel chroamtography (eluent,
petroleum ether:dichloromethane 80:20) to 73 (5.5 g, 57%) as
an oil: 1H NMR (400 MHz, CDCl3) δ 7.38-7.24 (m, 5 H, Ar),
3.47 (m, 2 H, H-1′), 3.30 (m, 2 H, H-6), 2.42 (t, 2 H, J ) 7.3
Hz, H-3′), 2.35 (m, 2 H, H-3), 3.85 (dt, 2 H, J ) 7.1 and 7.3,
H-2′), 1.76 (m, 4 H, H-4, H-5); 13C NMR (100 MHz, CDCl3) δ
169.89 (CO), 131.60, 128.30, 127.72, 123.87 (Ar), 89.39 (C-4′),
81.14 (C-5′), 48.37 (C-6), 46.67 (C-1′), 32.44 (C-3), 26.36 (C-
2′), 23.38 (C-5), 21.44 (C-4), 17.21 (C-3′). HRMS calcd for
C
16H19NO (M+): 241.1466. Found: 241.1466.
P en ta ca r bon ylch r om iu m Ca r ben e Com p lex 73. This
complex was obtained as above from lactam 71 (3 g, 12.5
mmol), and Cr(CO)6 as a yellow solid (2.63 g, 50.5%) after silica
gel chromatography (eluent, petroleum ether:dichloromethane
80:20); mp 38 °C; 1H NMR (400 MHz, CDCl3) δ 7.44-7.28 (m,
5 H, Ar), 4.28 (m, 2 H, H-1′), 3.52 (t, 2 H, J ) 6.1 Hz, H-6),
3.20 (t, 2 H, J ) 6.5 Hz, H-3), 2.62 (t, 2 H, J ) 6.7 Hz, H-3′),
1
2.11 (m, 2 H, H-2′), 1.81 (m, 2 H, H-5), 1.58 (m, 2 H, H-4); 13
C
68 as a solid (0.050 g, 30%): mp 225 °C; H NMR (400 MHz,
CDCl3) δ 7.77-7.15 (m, 10 H, Ar), 6.73 (s, 1 H), 6.70 (s, 1 H)
(H-8, H-11), 5.94 (s, 2 H, OCH2O), 5.01 (d, 1 H, J ) 16 Hz,
CHPh), 4.04 (d, 1 H, J ) 16 Hz, CHPh), 3.31 (d, 1 H, J ) 13.6
Hz, H-7), 3.20 (m, 1 H, H-11b), 3.17 (d, 1 H, J ) 13.6 Hz, H-3),
2.93 (m, 1 H, H-3), 2.58 (m, 1 H, H-3), 2.05 (m, 2 H, H-1, H-2),
1.87 (m, 1 H, H-1), 1.75 (m, 1 H, H-2); 13C NMR (100 MHz,
CDCl3) δ 172.19 (CO), 159.84 (C-3a), 146.92, 146.09 (C-9, C-10),
135.25 (C-4), 132.56-128.11 (C-9, C-10, Ar), 101.06 (OCO),
65.85 (C-11c), 44.56 (C-11b), 43.28 (C-7), 41.46 (CHPh), 26.00
(C-2), 23.44 (C-3). Anal. Calcd for C29H25NO3: C, 80.0, H,
5.75; N, 3.22. Found: C, 78.20, H, 5.82; N, 3.19.
NMR (100 MHz, CDCl3) δ 271.79 (CrdC), 223.46, 218.15 (CO),
131.68, 128.40, 128.05 (Ar), 87.83 (C-4′), 82.11 (C-5′), 63.84
(C-1′), 51.18 (C-6), 49.81 (C-3), 27.60 (C-2′), 21.76 (C-5), 17.26
(C-4), 16.83 (C-3′). Anal. Calcd for C21H19NO5Cr: C, 60.43;
H, 4.55; N, 3.35. Found: C, 60.34; H, 4.59; N, 3.24.
2-P h en yl-3,4,5,6,7,8,8a ,8b-octa h yd r o-5a -a za a cen a p h th -
ylen -1-on e (74). Thermolysis of complex (73) (2.0 g, 4.80
11c-Ben zyl-9,10-(m et h ylen ed ioxo)-4-(t r im et h ylsilyl)-
1,2,3,7,11b,11c-h exah ydr opyr r olo(3,2,1-de)ph en an th r idin -
5-on e
(69)
a n d
4-Ben zyl-9,10-(m et h ylen ed ioxo)-
1,2,3,7,11b,11c-h exah ydr opyr r olo(3,2,1-de)ph en an th r idin -
5-on e (70). Thermolysis of complex 66b (0.33 g, 0.555 mmol)
mmol) in refluxing benzene (60 mL) for 12 h led to compound
74 (0.22 g, 18%) after silica gel chromatography (elution,
petroleum ether:ethyl acetate 60:40): white solid; mp 42 °C;
IR (CHCl3, cm-1) 1703; 1H NMR (400 Mhz, CDCl3) δ 7.43-
7.31 (m, 5 H, Ar), 2.96 (dd, 1 H, J ) 13.7 and 4.5 Hz, H-3),
2.92 (d, 1 H, J ) 6.5 Hz, H-8b), 2.84 (d, 1 H, J ) 10.3 Hz,
H-11), 2.81-2.75 (m, 1 H, H-11), 2.29 (dt, 1 H, J ) 10.3 Hz,
H-8a), 2.32-2.22 (m, 3 H, H-5, H-3, H-6), 2.21-1.78 (m, 3 H,
H-4, H-8, H-7), 1.77-1.64 (m, 2 H, H-4, H-8), 1.60-1.50 (m, 1
H, H-7); 13C NMR (100 MHz, CDCl3) δ 207.64 (CO), 170.97
in refluxing benzene led to two compound, which were