1602, 1492, 1452, 1394, 1244, 1208, 1109, 1108; δH (400 MHz; CDCl3) 1.01-1.19 (1H, m, HA-7″), 1.22-1.26
ACCEPTED MANUSCRIPT
(3H, m, NCH(CH3)Ph), 1.29-1.44 (4H, m, H-4″, H-6″), 1.52-1.63 (4H, m, H-5″, H-8″), 1.71-1.80 (1H, m, HB-
7″), 1.89-2.08 (3H, m, HA-2″, H-3″, H-4a″), 2.13 (3H, s, 3ʹ-CH3), 2.52 (1H, d, J = 9.2 Hz, HB-2″), 3.10-3.17
(1H, m, H-8a″), 3.61 (1H, q, J = 6.5 Hz, NCH(CH3)Ph), 3.82-2.87 (1H, m, CHAHBO), 3.96-4.01 (1H, m,
CHAHBO), 6.45-6.46 (1H, m, H-4′), 7.21-7.39 (7H, m, H-5, H-6, Ar-H), 7.56-7.65 (2H, m, H-3, H-4); δC (100
MHz; CDCl3) 11.0 (3′-CH3), 17.4 (C-8″), 20.9 (C-6″), 21.0 (NCH(CH3)Ph), 25.5 (C-7″), 27.4 (C-4″), 31.7 (C-
5″), 35.2 (C-4a″), 36.2 (C-3″), 47.0 (C-2″), 55.3 (NCH(CH3)Ph), 60.5 (C-8a″), 70.0 (CH2O), 126.5 (Ar-CH),
127.0 (C-4′), 127.8 (C-1), 127.9 (Ar-CH), 128.2 (Ar-CH), 128.8 (C-5), 130.1 (C-6), 131.2 (C-3), 131.6 (C-2),
132.9 (C-4), 146.0 (C-3ʹ, Ar-C), 164.44 (COO), 169.4 (C-2ʹ), 170.7 (C-5ʹ); HRMS (EI+) m/z = [M]+
C30H34N2O4 requires 486.25186; found 486.25221.
4.5.4 ((3′′S*,4a′′R*,9a′′R*)-1′′-Benzyldecahydro-1I-cyclohepta[b]pyridin-3′′-yl)methyl 2-(3′-methyl-2′,5′-dioxo-
2′,5′-dihydro-1I-pyrrol-1′-yl)benzoate 10d. Using general method D alcohol 8d (0.120 g, 0.44 mmol) after
purification by flash chromatography (50% n-hexanes in ethyl acetate) gave title compound 10d (0.167 g, 78%)
as a light green oil. RF = 0.55 (3:1 ethyl acetate, n-hexanes,); νmax/cm-1 2930, 1715, 1497, 1453, 1371, 1260,
1072; δH (400 MHz; CDCl3) 0.94-1.19 (4H, m, HA-4ʹʹ, HA-5ʹʹ, HA-6ʹʹ, HA-7ʹʹ), 1.21-1.30 (1H, m, HA-8ʹʹ), 1.31-
1.40 (1H, m, HA-9ʹʹ), 1.50-1.61 (2H, m, HB-6ʹʹor HB-7ʹʹand 8ʹʹ-HB), 1.62-1.70 (1H, m, HB-9ʹʹ), 1.71-1.81 (2H, m,
HB-4ʹʹ and HB-6ʹʹ or HB-7ʹʹ), 1.85-1.94 (1H, m, HB-5ʹʹ), 1.95-2.00 (3H, m, HA-2ʹʹ, H-3ʹʹ, H-4aʹʹ), 2.15 (3H, s, 3ʹ-
CH3), 2.56 (1H, d, J = 9.2 Hz, HB-2ʹʹ), 2.77-2.83 (1H, m, H-9aʹʹ), 3.58-3.69 (2H, m, NCH2Ph), 3.91-4.05 (2H, m,
CH2O), 6.44 (1H, s, H-4ʹ), 7.19-7.35 (6H, m, H-6, Ar-H), 7.44 (1H, td, J = 1.4, 7.5 Hz, H-5), 7.61 (1H, td, J =
1.4, 7.5 Hz, H-4), 7.93 (1H, dd, J = 1.4, 7.5 Hz, H-3); δC (100 MHz, CDCl3) 11.1 (3ʹ-CH3), 19.8 (C-9ʹʹ), 23.3 (C-
8ʹʹ), 28.0 (C-4ʹʹ), 31.1, 31.4 (C-6ʹʹ, C-7ʹʹ), 33.7 (C-5ʹʹ), 36.0 (C-4aʹʹ), 37.0 (C-3ʹʹ), 49.1 (C-2ʹʹ), 58.8 (NCH2Ph),
62.1 (C-9aʹʹ), 68.1 (CH2O), 126.6 (Ar-CH), 127.8 (C-1), 128.1 (2 × Ar-CH), 128.5 (C-4ʹ), 128.8 (C-5), 130.2
(C-6), 131.4 (C-3), 131.5 (C-2), 133.0 (C-4), 139.5 (Ar-C), 146.1 (C-3ʹ), 164.7 (COO), 169.6 (C-2ʹ), 170.7 (C-
5ʹ); HRMS (EI+) m/z = [MH]+ C30H35N2O4 requires 487.2591; found 487.2580.
4.5.5 ((3′′S*,4a′′R*,9a′′R*)-1′′-(3-Phenylpropyl)decahydro-1H-cyclohepta[b]pyridin-3′′-yl)methyl 2-(3′-methyl-
2′,5′-dioxo-2′,5′-dihydro-1H-pyrrol-1′-yl)benzoate 10e. Using general method D alcohol 8e (0.120 g, 0.40
mmol) after purification by flash chromatography (50% n-hexanes in ethyl acetate) gave title compound 10e
(0.136 g, 64%) as a green oil. RF = 0.45 (1:1 ethyl acetate, n-hexanes,); νmax/cm-1 2928, 2853, 1709, 1585, 1449,
1256, 1134, 1085; δH (400 MHz; CDCl3) 0.93-1.04 (3H, m, HA-5ʹʹ and H-6ʹʹ or H-7ʹʹ), 1.13-1.19 (2H, m, H-4ʹʹ),
1.23-1.40 (2H, m, HA-8ʹʹ, HA-9ʹʹ), 1.50-1.62 (4H, m, HB-8ʹʹ, HB-9ʹʹ, and H-6ʹʹ or H-7ʹʹ), 1.74-1.84 (2H, m,
NCH2CH2CH2Ph), 1.90-2.03 (4H, m, HA-2ʹʹ, H-3ʹʹ, H-4aʹʹ, HB-5ʹʹ), 2.16 (3H, s, 3ʹ-CH3), 2.46 (2H, t, J = 7.4 Hz,
NCH2CH2CH2Ph), 2.57 (1H, d, J = 7.4 Hz, HB-2ʹʹ), 2.63 (2H, t, J = 7.3 Hz, NCH2CH2CH2Ph), 2.80-2.86 (1H,
m, H-9aʹʹ), 3.97-4.07 (2H, m, CH2O), 6.47 (1H, s, H-4ʹ), 7.16-7.32 (6H, m, H-6, Ar-H), 7.50 (1H, td, J = 1.3, 7.7
Hz, H-5), 7.64 (1H, td, J = 1.3, 7.7 Hz, H-4), 8.06 (1H, dd, J = 1.3, 7.7 Hz, H-3); δC (100 MHz, CDCl3) 11.2 (3ʹ-
CH3), 19.1 (C-9ʹʹ), 23.3 (C-8ʹʹ), 28.3 (C-4ʹʹ), 29.6 (NCH2CH2CH2Ph), 31.2, 31.5 (C-6ʹʹ, C-7ʹʹ), 33.8 (C-5ʹʹ,
NCH2CH2CH2Ph), 36.1 (C-4aʹʹ), 37.1 (C-3ʹʹ), 49.9 (C-2ʹʹ), 53.9 (NCH2CH2CH2Ph), 61.8 (C-9aʹʹ), 68.3 (CH2O),
125.6 (Ar-CH), 127.9 (C-1), 128.1 (Ar-CH), 128.3 (Ar-CH), 128.4 (C-4ʹ), 128.9 (C-5), 130.1 (C-6), 131.5 (C-3),
131.8 (C-2), 133.3 (C-4), 142.5 (Ar-C), 146.2 (C-3ʹ), 164.9 (COO), 169.6 (C-2ʹ), 170.7 (C-5ʹ); HRMS (EI+) m/z
= [MH]+ C32H39N2O4 requires 515.2904; found 515.2902.
4.5.6 ((3′′S,4a′′R,9a′′R)-1′′-((R)-1-Phenylethyl)decahydro-1H-cyclohepta[b]pyridin-3′′-yl)methyl 2-(3′-methyl-
2′,5′-dioxo-2′,5′-dihydro-1H-pyrrol-1′-yl)benzoate 10f. Using general method D alcohol 8f (0.080 g, 0.28 mmol)
after purification by flash chromatography (50% n-hexanes in ethyl acetate) gave title compound 10f (0.122 g,
20
88%) as a tan oil. [α]D +28 (c 1.0, CHCl3); RF = 0.35 (1:1 ethyl acetate, n-hexanes,); νmax/cm-1 2929, 1709,
1495, 1451, 1375, 1256, 1083; δH (400 MHz; CDCl3) 1.27 (3H, d, J = 6.7 Hz, NCH(CH3)Ph), 1.34-1.45 (2H, m,
HA-8ʹʹ, HA-9ʹʹ), 1.53-1.68 (4H, m, H-6ʹʹor H-7ʹʹ, HB-8ʹʹ, HB-9ʹʹ), 1.79-1.90 (6H, m, HA-2ʹʹ, H-4ʹʹ, H-4aʹʹ, H-6ʹʹ or
H-7ʹʹ), 1.94-2.03 (2H, m, H-5ʹʹ), 2.04-2.12 (1H, m, H-3ʹʹ), 2.49 (3H, d, J = 8.3 Hz, 3ʹ-CH3), 3.21-3.27 (1H, m,
NCH(CH3)Ph), 3.56-3.63 (1H, m, H-9aʹʹ), 3.75-3.84 (1H, m, OCHAHB), 3.92-3.97 (1H, m, OCHAHB), 7.15-7.41
(6H, m, H-4ʹ, H-2, H-3, Ar-H), 7.48-7.65 (2H, m, H-4, H-5); δC (100 MHz, CDCl3) 11.2 (3ʹ-CH3), 19.6 (C-9ʹʹ),
22.1 (NCH(CH3)Ph), 23.5 (C-8ʹʹ), 27.9 (C-4ʹʹ), 31.4, 31.9 (C-6ʹʹ, C-7ʹʹ), 34.2 (C-5ʹʹ), 36.2 (C-4aʹʹ), 37.3 (C-3ʹʹ),
48.0 (C-2ʹʹ), 57.9 (NCH(CH3)Ph), 61.2 (C-9aʹʹ), 127.8 (Ar-CH), 127.9 (C-4ʹ), 128.0 (Ar-CH) 128.8 (Ar-CH),
129.3 (C-5), 131.4 (C-6), 131.6 (C-3), 133.0 (C-4), 146.1 (C-3ʹ, Ar-C), 164.7 (COO), 169.6 (C-2ʹ), 170.6 (C-5ʹ);
HRMS (EI+) m/z = [MH]+ C31H37N2O4 requires 501.2740; found 501.2748.
15