B. Furman, G. Lipner / Tetrahedron 64 (2008) 3464e3470
3469
(m, 1H), 2.29e2.43 (m, 2H), 2.48e2.57 (m, 2H), 2.74 (dd,
4.4.5. (4R*,9aR*)-4-(Benzyloxymethyl)-1,3,4,6,7,9a-
J¼2.0, 15.0 Hz, 1H), 2.90 (dd, J¼6.4, 15.0 Hz, 1H), 2.98
(ddd, J¼2.9, 5.6, 11.7 Hz, 1H), 3.52e3.56 (m, 1H), 4.33 (dd,
J¼3.9, 6.4 Hz, 1H), 5.43 (ddd, J¼2.1, 4.0, 9.9 Hz, 1H),
5.70e5.82 (m, 1H), 7.20e7.35 (m, 5H); 13C NMR (CDCl3,
125 MHz) d 25.2, 46.0, 46.5, 47.3, 52.0, 63.7, 125.5, 127.6,
128.2, 128.4, 128.5, 138.6, 209.4; HRMS (ESI) calcd for
C17H22NO2 (MþHþ) 228.1383, found 228.1388.
hexahydro-2H-quinolizin-2-one (18e)
Chromatography (30:70 AcOEt/hexane) afforded 0.109 g
(80%) of a yellow oil: IR (neat) 3029, 2906, 1716,
;
1131 cmꢁ1 1H NMR (CDCl3, 500 MHz) d 2.08e2.16 (m,
1H), 2.24 (dd, J¼11.5, 14.6 Hz, 1H), 2.30e2.38 (m, 2H),
2.48 (dt, J¼2.1, 14.5 Hz, 1H), 2.70 (dd, J¼7.23, 14.5 Hz,
1H), 2.86 (ddd, J¼4.4, 8.9, 11.3 Hz, 1H), 2.93 (ddd, J¼3.4,
5.7, 11.3 Hz, 1H), 3.38e3.46 (m, 1H), 3.53 (dd, J¼4.6,
9.8 Hz, 1H), 3.63 (dd, J¼4.8, 9.8 Hz, 1H), 3.70e3.72 (m,
1H), 4.87 (d, J¼1.3 Hz, 2H), 5.45 (ddd, J¼2.2, 4.1, 9.9 Hz,
1H), 5.75e5.77 (m, 1H), 7.27e7.36 (m, 5H); 13C NMR
(CDCl3, 125 MHz) d 26.6, 43.5, 46.1, 47.2, 53.5, 61.3, 69.1,
73.5, 124.9, 127.5, 127.6, 128.4, 129.4, 138.0, 208.5; HRMS
(ESI) calcd for C17H22NO2 (MþHþ) 272.1645, found
272.1641.
4.4.2. (4R*,9aR*)-4-p-Tolyl-1,3,4,6,7,9a-hexahydro-2H-
quinolizin-2-one (18b)
Chromatography (30:70 AcOEt/hexane) afforded 0.097 g
1
(80%) of a yellow oil: IR (neat) 3027, 2917, 1714 cmꢁ1; H
NMR (CDCl3, 500 MHz) d 2.05e1.97 (m, 1H), 2.33 (s, 3H),
2.38 (ddd, J¼1.2, 10.4, 15.0 Hz, 1H), 2.46 (ddd, J¼4.5, 9.4,
11.7 Hz, 1H), 2.55 (ddd, J¼1.9, 4.0, 15.0 Hz, 1H), 2.71
(ddd, J¼1.9, 3.7, 15.0 Hz, 1H), 2.90 (ddd, J¼1.2, 6.6,
15.0 Hz, 1H), 2.96 (ddd, J¼2.6, 5.6, 11.5 Hz, 1H), 3.48e
3.52 (m, 1H), 4.30 (dd, J¼3.7, 6.5 Hz, 1H), 5.41 (ddd,
J¼2.1, 4.0, 9.9 Hz, 1H), 5.72e5.78 (m, 1H), 7.01e7.26 (m,
4H); 13C NMR (CDCl3, 125 MHz) d 21.0, 25.3, 46.1, 46.6,
47.4, 51.9, 63.4, 125.4, 128.4, 128.6, 128.9, 135.5, 137.3,
209.6; HRMS (EI) calcd for C16H19NO (Mþ) 241.1467, found
241.1458.
4.4.6. (4R*,9aR*)-4-Cyclohexyl-1,3,4,6,7,9a-hexahydro-
2H-quinolizin-2-one (18f)
Chromatography (20:80 AcOEt/hexane) afforded 0.096 g
(82%) of a colorless oil: IR (neat) 3072, 2915, 1712 cmꢁ1
;
1H NMR (CDCl3, 500 MHz) d 0.78e0.92 (m, 2H), 1.05e
1.25 (m, 3H), 1.30e2.11 (m, 6H), 2.21 (ddd, J¼2.0, 3.5,
14.1 Hz, 1H), 2.34e2.46 (m, 3H), 2.55 (dd, J¼6.1, 13.5 Hz,
1H), 2.66 (dd, J¼2.6, 6.0, 11.2 Hz, 1H), 2.80 (ddd, J¼2.7,
6.1, 9.6 Hz, 1H), 3.09e3.11 (m, 1H), 3.55e3.60 (m, 1H),
5.57e5.78 (m, 2H); 13C NMR (CDCl3, 125 MHz) d 26.1,
26.2, 26.5, 26.7, 30.3, 30.4, 38.5, 39.6, 43.9, 45.5, 53.0,
68.7, 125.4, 128.8, 209.9; HRMS (ESI) calcd for
C15H24NO2 (MþHþ) 234.1852, found 234.1856.
4.4.3. (4R*,9aR*)-4-(Fluorophenyl)-1,3,4,6,7,9a-hexa-
hydro-2H-quinolizin-2-one (18c)
Chromatography (30:70 AcOEt/hexane) afforded 0.093 g
1
(76%) of a yellow oil: IR (neat) 3020, 2915, 1724 cmꢁ1; H
NMR (CDCl3, 400 MHz) d 2.00e2.09 (m, 1H), 2.31e2.36
(m, 1H), 2.40 (ddd, J¼1.1, 10.2, 14.9 Hz, 1H), 2.47 (ddd,
J¼4.7, 9.4, 11.7 Hz, 1H), 2.55 (ddd, J¼1.8, 4.0, 15.0 Hz,
1H), 2.71 (ddd, J¼1.8, 4.0, 15 Hz, 1H), 2.90 (ddd, J¼1.2,
6.5, 15.0 Hz, 1H), 2.97 (ddd, J¼3.2, 5.5, 11.6 Hz, 1H),
3.46e3.52 (m, 1H), 4.33 (dd, J¼4.0, 6.5 Hz, 1H), 5.44 (ddd,
J¼2.2, 4.1, 10.0 Hz, 1H), 5.75e5.79 (m, 1H), 6.98e7.05 (m,
2H), 7.11e7.23 (m, 2H); 13C NMR (CDCl3, 100 MHz)
d 25.1, 45.9, 46.4, 47.1, 52.0, 63.0, 115.0, 115.2, 125.6,
128.6, 128.4, 129.8, 129.9, 134.5, 160.9, 163.4, 209.3;
HRMS (ESI) calcd for C15H17NOF (MþHþ) 246.1289, found
246.1303.
4.4.7. (4R*,9aR*)-Ethyl 2,3,4,6,7,9a-hexahydro-2-oxo-2H-
quinolizine-4-carboxylate (18g)
Chromatography (20:80 AcOEt/hexane) afforded 0.088 g
(79%) of a colorless oil: IR (neat) 2916, 1736, 1727,
1181 cmꢁ1
; d 1.27 (t,
1H NMR (CDCl3, 500 MHz)
J¼7.1 Hz, 2H), 2.03e2.11 (m, 1H), 2.21 (ddd, J¼0.6, 11.8,
14.8 Hz, 1H), 2.38e2.46 (m, 2H), 2.55 (dt, J¼2.0, 15.0 Hz,
1H), 2.71 (ddd, J¼0.8, 6.8, 15.0 Hz, 1H), 2.81 (dt, J¼11.1,
15.2 Hz, 1H), 2.99 (dd, J¼6.0, 11.6 Hz, 1H), 3.63e3.67 (m,
1H), 3.88 (dd, J¼1.6, 6.8 Hz, 1H), 4.16e4.19 (m, 1H),
5.42e5.78 (m, 2H); 13C NMR (CDCl3, 125 MHz) d 14.4,
26.6, 42.9, 46.5, 48.7, 53.0, 60.8, 63.8, 124.8, 128.9, 170.4,
206.2; HRMS (EI) calcd for C12H18NO3 (MþHþ) 224.1281,
found 224.1289.
4.4.4. (4R*,9aR*)-4-(3,4-Dimethoxyphenyl)-1,3,4,6,7,9a-
hexahydro-2H-quinolizin-2-one (18d)
Chromatography (30:70 AcOEt/hexane) afforded 0.112 g
(78%) of an orange oil; IR (neat) 3017, 2913, 1720 cmꢁ1
;
1H NMR (CDCl3, 500 MHz) d 1.99e2.07 (m, 1H), 2.27e
2.36 (m, 1H), 2.39 (ddd, J¼1.2, 10.0, 14.8 Hz, 1H), 2.50e
2.58 (m, 2H), 2.73 (ddd, J¼1.9, 4.1, 14.9 Hz, 1H), 2.88
(ddd, J¼1.3, 6.3, 14.9 Hz, 1H), 2.98 (ddd, J¼3.0, 5.6,
11.8 Hz, 1H), 3.55 (m, 1H), 3.86 (2ꢂs, 6H), 4.28 (dd,
J¼4.1, 6.4 Hz, 1H), 5.44 (ddd, J¼2.1, 4.1, 9.9 Hz, 1H),
5.75e5.79 (m, 1H), 6.73e6.82 (m, 3H); 13C NMR (CDCl3,
125 MHz) d 25.1, 46.3, 46.5, 47.2, 52.2, 55.9, 63.3, 110.7,
111.6, 120.6, 125.5, 128.5, 131.5, 148.5, 148.7, 209.6;
HRMS (EI) calcd for C17H21NO3 (Mþ) 287.1521, found
287.1525.
4.4.8. (4R*,10aR*)-1,3,4,7,8,10a-Hexahydro-4-phenyl-
pyrido[1,2-a]azepin-2-one (18h)
Chromatography (30:70 AcOEt/hexane) afforded 0.021 g
1
(32%) of a yellow oil: IR (neat) 2920, 1715 cmꢁ1; H NMR
(CDCl3, 500 MHz) d 1.05e1.15 (m, 1H), 1.48e1.58 (m,
1H), 2.23e2.31 (m, 2H), 2.41 (dt, J¼2.6, 13.4 Hz, 1H), 2.46
(ddd, J¼2.4, 4.0, 14.5 Hz, 1H), 2.55 (dd, J¼10.2, 14.4 Hz,
1H), 2.86 (ddd, J¼2.2, 11.9, 14.8 Hz, 1H), 2.93 (dd, J¼5.5,
13.4 Hz, 1H), 3.12e3.17 (m, 1H), 4.21 (dd, J¼3.9, 10.1 Hz,
1H), 5.51 (ddd, J¼2.3, 4.5, 11.0 Hz, 1H), 6.03e6.07 (m,
1H), 7.25e7.37 (m, 5H); 13C NMR (CDCl3, 125 MHz)