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K. Van Emelen et al. / Tetrahedron 58 #2002) 4225±4236
J8 Hz), 6.85 9d, 1H, J8 Hz), 4.73 9s, 1H), 4.47 9t, 1H,
J6 Hz), 4.11 9br d, 2H, J6 Hz), 3.84 9s, 3H), 3.35 9d, 1H,
J16 Hz), 2.97 9d, 1H, J16 Hz), 2.92 9br d, 1H, J12 Hz),
2.76 9ddd, 1H, J12, 12, 2 Hz), 2.62 9br d, 1H, J14 Hz),
2.00 9br s, 1H), 1.70 9m, 1H), 1.35 9m, 2H); 13C NMR
9100 MHz, CDCl3, ppm): d 21.3, 31.9, 40.5, 41.6, 43.2,
55.2, 62.2, 77.0, 110.1, 120.6, 122.7, 125.5, 127.1, 127.4,
127.5, 127.8, 128.3, 128.5, 128.9, 156.1, 156.8; EIMS
[m/z 9%)]: 428 9M1, 0.2), 249 9M12HNCONHCH2C6H4±
o-OCH3, 6), 248 9M12H2NCONHCH2C6H4±o-OCH3,
132.5, 141.9, 146.3, 159.8, 172.9; EIMS [m/z 9%)]: 351
9M1, 34), 333 9M12H2O, 70), 311 9M12CH2CN, 36),
2919M 12HCO2CH3, 32), 279 9M12CH2CN±CH3OH,
36), 2519M 12HCO2CH3±CH2CN, 54), 237 9M12
HCO2CH3±CH2CH2CN, 51), 105 9C6H5CO1, 100), 77
9C6H51, 50); HRMS: calculated for C21H21NO4 351.1471,
found 351.1470; Anal. calcd: C 71.78; H 6.02; N 3.99.
Found: C 71.57; H 6.12; N 3.96.
4.4.4. cis-44aRp,9bRp) Methyl 8-methoxy-2-oxo-9b-
phenyl-1,2,3,4,5,9b-hexahydro-4aH-indeno[1,2-b]pyridine-
4a-carboxylate 419). This was puri®ed by column chroma-
tography 997:3 CH2Cl2/MeOH) and crystallisation from
EtOH. Yield: 76%; mp 98C): 333±334; IR 9KBr, cm21):
100), 121 9CH2C6H4±o-OCH31, 7), 919C H71, 14), 77
7
9C6H51, 6); HRMS: calculated for C18H17N 248.1439,
found 248.1424; Anal. calcd: C 75.85; H 6.84; N 9.83.
Found: C 75.56; H 6.83; N 9.64.
1
3448, 3058, 2953, 2850, 1724, 1662; H NMR 9400 MHz,
CDCl3, ppm): d 7.20 9m, 4H), 6.90 9m, 3H), 6.60 9d, 1H,
J2 Hz), 6.54 9s 9br), 1H), 3.78 9d, 1H J15 Hz), 3.73 9s,
3H), 3.30 9s, 3H), 2.82 9d, 1H, J15 Hz), 2.50 9ddd, 1H,
J17, 10, 4 Hz), 2.25 9m, 2H), 2.07 9ddd, 1H, J16, 10,
4 Hz); 13C NMR 9100 MHz, CDCl3, ppm): d 28.6, 29.3,
30.9, 51.9, 55.4, 59.1, 60.0, 110.7, 118.9, 124.4, 127.5,
128.3, 128.5, 130.0, 139.7, 142.8, 160.5, 171.1, 172.0;
EIMS [m/z 9%)]: 3519M 1, 12), 323 9M12CO, 6), 295
9M12CH2CH2CO, 100), 264 9M12CH2CH2CO±OCH3,
14), 236 9M12CH2CH2CO±CO2CH3, 100); HRMS: calcu-
lated for C21H21NO4 351.1471, found 351.1470; Anal.
calcd: C 71.78; H 6.02; N 3.99. Found: C 71.56; H 6.22;
N 3.86.
4.4. Preparation of phenolic compound 1
Starting from 6-methoxy 1-indanone, compound 19 was
prepared according to the procedure given for compound
3a.
4.4.1. cis-44aRp,9bRp) Methyl 6-methoxy-1-oxo-2-indane-
carboxylate 416). This was puri®ed by column chroma-
tography 97:3 hexanes/EtOAc) followed by crystallisation
from i-PrOH. Yield: 91%; mp 98C): 74±75; IR 9KBr, cm21):
1
3448, 3014, 2949, 2845, 1735, 1710; H NMR 9400 MHz,
CDCl3, ppm): d 7.38 9d, 1H, J8 Hz), 7.23 9m, 2H), 3.84 9s,
3H), 3.79 9s, 3H), 3.75 9dd,1H, J16, 3 Hz), 3.47 9dd,
1H, J8, 3 Hz), 3.30 9dd, 1H, J16, 8 Hz); 13C NMR
9100 MHz, CDCl3, ppm): d 29.6, 52.7, 53.9, 55.7, 105.7,
124.0, 127.2, 136.4, 146.5, 159.8, 169.6, 199.3; EIMS [m/z
9%)]: 220 9M1, 47), 188 9M12HOCH3, 20), 161 9M12
CO2CH3, 42), 160 9M12HCO2CH3, 100); HRMS: calcu-
lated for C12H12O4 220.0736, found 220.0734.
4.4.5. cis-44aRp,9bRp)-8-Methoxy-2-oxo-9b-phenyl-1,2,3,
4,5,9b-hexahydro-4aH-indeno[1,2-b]pyridine-4a-carb-
oxylic acid 420). This was puri®ed by column chroma-
tography
crystallisation from EtOH. Yield: 70%; mp 98C): 309±
938.5:12:0.5
CH2Cl2/EtOAc/AcOH)
and
311; IR 9KBr, cm21): 3391, 3246, 3019, 2933, 2850,
1731, 1661; H NMR 9400 MHz, CD3OD, ppm): d 7.25±
1
4.4.2. cis-44aRp,9bRp) Methyl 2-4cyanoethyl)-6-methoxy-
1-oxo-2-indanecarboxylate 417). This was puri®ed by
column chromatography 97:3 hexanes/EtOAc). Yield:
7.20 9m, 4H), 7.05±7.03 9m, 2H), 6.90 9dd, 1H, J8, 2 Hz),
6.85 9d, 1H, J2 Hz), 3.73 9s, 3H), 3.59 9d, 1H, J16 Hz),
2.96 9ddd, 1H, J18, 12, 6 Hz), 2.77 9d, 1H, J16 Hz), 2.29
9ddd, 1H, J18, 6, 3 Hz), 2.16 9ddd, 1H, J14, 6, 3 Hz),
2.03 9ddd, 1H, J14, 12, 6 Hz); 13C NMR 9100 MHz,
CD3OD, ppm): d 29.2, 30.3, 40.1, 55.9, 57.8, 74.4, 110.0,
116.4, 126.8, 128.7, 128.8, 128.9, 132.8, 142.2, 148.9,
161.6, 175.0, 175.7; EIMS [m/z 9%)]: 337 9M1, 13), 309
9M12CO, 31), 293 9M12CO2, 40), 2819M 12CH2CH2CO,
100), 280 9M12CH2CONH, 94), 234 9M12OCH3±
CH2CH2CONH2, 37); HRMS: calculated for C20H19NO4
337.1314, found 337.1312; Anal. calcd: C 71.20; H 5.68;
N 4.15. Found: C 70.95; H 5.53; N 3.95.
76%; IR 9NaCl, cm21): 2954, 2840, 2248, 1740, 1708; H
1
NMR 9400 MHz, CDCl3, ppm): d 7.40 9d, 1H, J9 Hz),
7.25 9dd, 1H, J9, 2 Hz), 7.18 9d, 1H, J2 Hz), 3.83 9s,
3H), 3.69 9s, 3H), 3.62 9d, 1H, J16 Hz), 3.08 9d, 1H,
J16 Hz), 2.58 9m, 2H), 2.37 9m, 1H), 2.25 9m, 1H); 13C
NMR 9100 MHz, CDCl3, ppm): d 12.7, 30.0, 36.3, 52.6,
55.3, 59.2, 105.6, 118.9, 125.0, 126.9, 135.4, 145.0, 159.7,
170.3, 200.7; EIMS [m/z 9%)]: 273 9M1, 80), 241
9M12HOCH3, 32), 213 9M12HCO2CH3, 60), 173 9M12
HCO2CH3±CH2CN, 100); HRMS: calculated for
C15H15NO4 273.1001, found 273.1002.
4.4.6. cis-44aRp,9bRp) Methyl N-48-methoxy-2-oxo-9b-
phenyl-1,2,3,4,5,9b-hexahydro-4aH-indeno[1,2-b] pyridin-
4-yl)carbamate 421). This was puri®ed by column chroma-
tography 9EtOAc) and crystallisation from CH2Cl2/hexanes.
Yield: 90%; mp 98C): 255±256; IR 9KBr, cm21): 3383,
3051, 2934, 2851, 1713, 1660; 1H NMR 9400 MHz,
CDCl3, ppm): d 7.40±7.36 9m, 3H), 7.22 9d, 1H, J8 Hz),
7.07±7.05 9m, 2H), 6.90 9dd, 1H, J8, 2 Hz), 6.62 9d, 1H,
J2 Hz), 6.45 9s 9br), 1H), 3.75 9s, 3H), 3.53 9s, 3H), 3.45
9d, 1H, J16 Hz), 3.08 9d, 1H, J16 Hz), 2.79 9ddd, 1H,
J18, 4, 4 Hz), 2.62 9ddd, 1H, J18, 12, 5 Hz), 2.33 9ddd,
1H, J18, 5, 4 Hz), 2.01 9ddd, 1H, J18, 12, 4 Hz), 1.58 9s,
1H); 13C NMR 9100 MHz, CDCl3, ppm): d 27.4, 27.5, 41.9,
4.4.3. cis-44aRp,9bRp) Methyl 2-4cyanoethyl)-1-hydroxy-
6-methoxy-1-phenyl-2-indanecarboxylate 418). This was
puri®ed by column chromatography 97:3 hexanes/EtOAc)
and crystallisation from i-PrOH. Yield: 88%; mp 98C):
145±148; IR 9KBr, cm21): 3420, 3030, 2950, 2839, 2255,
1
1723; H NMR 9400 MHz, CDCl3, ppm): d 7.25 9m, 5H),
7.13 9dd, 1H, J8, 2 Hz), 6.90 9dd, 1H, J8, 2 Hz), 6.65 9d,
1H, J2 Hz), 3.72 9s, 3H), 3.54 9d, 1H, J16 Hz), 3.23 9s,
3H), 2.87 9d, 1H, J16 Hz), 2.73 9s 9br), 1H), 2.55 9ddd, 1H,
J13, 10, 6 Hz), 2.32 9ddd, 1H, J17, 10, 6 Hz), 2.26 9ddd,
1H, J17, 10, 6 Hz), 2.16 9ddd, 1H, J13, 10, 6 Hz); 13C
NMR 9100 MHz, CDCl3, ppm): d 14.0, 28.7, 36.3, 51.7,
55.4, 64.9, 108.8, 116.0, 119.5, 125.7, 126.0, 127.8, 127.9,