13
J = 8.5, Í-4), 7.87 (2H, d, J = 9.1, H-2ꢄ, 6ꢄ). C NMR spectrum (125 MHz, DMSO-d , ꢂ, ppm): 14.57, 24.67, 27.10, 34.28,
6
49.35, 50.59, 58.79, 59.74, 63.34, 104.02, 105.70, 110.87, 112.64, 112.68, 115.03, 115.71, 124.38, 124.49, 133.02, 138.75,
146.09, 151.15, 159.74, 162.18, 165.57, 165.61, 181.43.
Methyl 4-{(Z)-[6-Hydroxy-3-oxo-7-{[(1R,5S)-8-oxo-1,5,6,8-tetrahydro-2H-1,5-methanopyrido[1,2-
a][1,5]diazocin-3(4H)-yl]methyl}-1-benzofuran-2(3H)-ylidene]methyl}benzoate (3c). C H N O , yield 65%, mp 196–
29 26
2 6
+
1
198ꢃÑ. MS(CI): 499.2 [M + H] (100%). Í NMR spectrum (400 MHz, DMSO-d , ꢂ, ppm, J/Hz): cytisine protons: 1.69–1.85
6
(2H, m, H-8), 2.40–2.60 (3H, m, H-9, 11à, 13à), 2.95–3.11 (3H, m, H-7, 11b, 13b), 3.66–3.91 (4H, m, H-10, N(12)-CH -Ar),
2
6.06 (1H, d, J = 6.8, Í-5), 6.16 (1H, d, J = 9.0, Í-3), 7.23 (1H, dd, J = 9.0, 6.8, Í-4); aurone protons: 3.89 (3H, s, 4ꢄ-ÑÎÎÑÍ ),
3
13
6.64 (1H, d, J = 8.4, Í-5), 6.81 (1H, s, Í-2à), 7.53 (1H, d, J = 8.4, Í-4), 7.96–8.07 (4H, m, Í-2ꢄ, 3ꢄ, 5ꢄ, 6ꢄ). C NMR spectrum
(100 MHz, DMSO-d , ꢂ, ppm): 24.69, 27.10, 34.28, 49.36, 50.32, 52.32, 58.79, 59.72, 103.97, 106.15, 108.68, 112.10,
6
112.96, 115.53, 115.65, 124.80, 124.86, 129.61, 131.06, 136.81, 138.70, 148.44, 151.23, 162.16, 165.79, 166.20, 181.58.
(1R,5S)-3-{[(2Z)-6-Hydroxy-2-(3-methoxybenzylidene)-3-oxo-2,3-dihydro-1-benzofuran-7-yl]methyl}-
1,2,3,4,5,6-hexahydro-8H-1,5-methanopyrido[1,2-a][1,5]diazocin-8-one (3d). C H N O , yield 68%, mp 207–209ꢃÑ.
28 26
2 5
+
1
MS(CI): 471.2 [M + H] (100%). Í NMR spectrum (400 MHz, DMSO-d , ꢂ, ppm, J/Hz): cytisine protons: 1.66–1.84 (2H,
6
m, H-8), 2.37–2.57 (3H, m, H-9, 11à, 13à), 2.95–3.11 (3H, m, H-7, 11b, 13b), 3.64–3.86 (4H, m, H-10, N(12)-CH -Ar), 6.06
2
(1H, dd, J = 6.9, 1.4, H-5), 6.19 (1H, dd, J = 9.0, 1.4, H-3), 7.28 (1H, dd, J = 9.0, 6.8, H-4); aurone protons: 3.84 (3H, s,
3ꢄ-OCH ), 6.65 (1H, d, J = 8.4, H-5), 6.76 (1H, s, H-2a), 6.99–7.07 (1H, m, H-4ꢄ), 7.42 (1H, t, J = 7.9, H-5ꢄ), 7.47–7.57 (3H,
3
13
m, H-4, 2ꢄ, 6ꢄ). C NMR spectrum (125 MHz, DMSO-d , ꢂ, ppm): 24.61, 27.09, 34.27, 49.32, 50.35, 55.15, 58.77, 59.70, 103.95,
6
105.81, 110.33, 112.27, 112.81, 115.61, 115.67, 115.87, 123.72, 124.66, 130.01, 133.36, 138.70, 147.40, 151.20, 159.40,
162.14, 165.88, 166.04, 181.61.
(1R,5S)-3-{[(2Z)-6-Hydroxy-2-(3,4-dimethoxybenzylidene)-3-oxo-2,3-dihydro-1-benzofuran-7-yl]methyl}-
1,2,3,4,5,6-hexahydro-8H-1,5-methanopyrido[1,2-a][1,5]diazocin-8-one (3e). C H N O , yield 65%, mp 227–229ꢃÑ.
29 28
2 6
+
1
MS(CI): 501.2 [M + H] (100%). Í NMR spectrum (400 MHz, DMSO-d , ꢂ, ppm, J/Hz): cytisine protons: 1.66–1.85 (2H,
6
m, H-8), 2.37–2.48 (3H, m, H-9, 11à, 13à), 2.95–3.09 (3H, m, H-7, 11b, 13b), 3.66–3.88 (4H, m, H-10, N(12)-CH -Ar), 6.07
2
(1H, d, J = 6.8, Í-5), 6.20 (1H, d, J = 9.1, Í-3), 7.29 (1H, dd, J = 9.0, 6.8, Í-4); aurone protons: 3.84, 3.85 (each 3Í, s,
3ꢄ, 4ꢄ-OCH ), 6.63 (1H, d, J = 8.4, Í-5), 6.76 (1H, s, H-2a), 7.09 (1H, d, J = 8.4, H-5ꢄ), 7.48 (1H, d, J = 1.9, H-2ꢄ), 7.51 (1H,
3
13
d, J = 8.4, H-4), 7.62 (1H, d, J = 1.9, H-6ꢄ). C NMR spectrum (100 MHz, DMSO-d , ꢂ, ppm): 24.66, 27.09, 34.25, 49.36,
6
50.50, 55.42, 55.61, 58.91, 59.74, 104.01, 105.63, 111.26, 111.92, 112.62, 112.68, 113.46, 115.73, 124.48, 124.79, 125.54,
138.75, 146.14, 148.71, 150.38, 151.22, 162.19, 165.50, 165.62, 181.39.
(1R,5S)-3-{[(2Z)-6-Hydroxy-3-oxo-2-(3,4,5-trimethoxybenzylidene)-2,3-dihydro-1-benzofuran-7-yl]methyl}-
1,2,3,4,5,6-hexahydro-8H-1,5-methanopyrido[1,2-a][1,5]diazocin-8-one (3f). C H N O , yield 81%, mp 206–207ꢃÑ.
30 30
2 7
+
1
MS(CI): 531.2 [M + H] (100%). Í NMR spectrum (500 MHz, DMSO-d , ꢂ, ppm, J/Hz): cytisine protons: 1.65–1.83 (2H,
6
m, H-8), 2.35–2.47 (3H, m, H-9, 11à, 13à), 2.92–3.09 (3H, m, H-7, 11b, 13b), 3.67–3.89 (4H, m, H-10, N(12)-CH -Ar), 6.05
2
(1H, d, J = 6.9, Í-5), 6.20 (1H, d, J = 8.9, Í-3), 7.30 (1H, dd, J = 8.9, 6.9, Í-4); aurone protons: 3.74 (3H, s, 4ꢄ-OCH ), 3.85
3
13
(6H, s, 3ꢄ, 5ꢄ-OCH ), 6.65 (1H, d, J = 8.3, Í-5), 6.76 (1H, s, H-2a), 7.32 (2H, s, H-2ꢄ, 6ꢄ), 7.52 (1H, d, J = 8.3, H-4). C NMR
3
spectrum (125 MHz, DMSO-d , ꢂ, ppm): 24.65, 27.08, 34.24, 49.34, 50.29, 55.91, 58.93, 59.70, 60.19, 103.92, 105.70,
6
108.61, 110.82, 112.27, 112.82, 115.69, 124.61, 127.56, 138.68, 139.00, 146.82, 151.27, 152.94, 162.16, 165.75, 165.87,
181.43.
(1R,5S)-3-({(2Z)-6-Hydroxy-2-[2-(difluoromethoxy)benzylidene]-3-oxo-2,3-dihydro-1-benzofuran-7-yl}methyl)-
1,2,3,4,5,6-hexahydro-8H-1,5-methanopyrido[1,2-a][1,5]diazocin-8-one (3g). C H F N O , yield 53%, mp 214–216ꢃÑ.
28 24 2
2 5
+
1
MS(CI): 507.2 [M + H] (100%). Í NMR spectrum (400 MHz, DMSO-d , ꢂ, ppm, J/Hz): cytisine protons: 1.67–1.87 (2H, m,
6
H-8), 2.40–2.58 (3H, m, H-9, 11à, 13à), 2.93–3.09 (3H, m, H-7, 11b, 13b), 3.64–3.86 (4H, m, H-10, N(12)-CH -Ar), 6.06
2
(1H, dd, J = 6.9, 1.4, H-5), 6.17 (1H, dd, J = 9.0, 1.4, H-3), 7.25 (1H, dd, J = 9.0, 6.6, Í-4); aurone protons: 6.65 (1H, d, J = 8.5,
Í-5), 6.86 (1H, s, H-2a), 7.30–7.34 (1H, m, H-3ꢄ), 7.35 (1H, t, J = 73.5, 2ꢄ-OCHF ), 7.39–7.48, 7.48–7.58 (1H, 2H, m,
CF
2
13
Í-4, 4ꢄ, 5ꢄ), 8.21 (1H, dd, J = 7.9, 1.7, Í-6ꢄ). C NMR spectrum (100 MHz, DMSO-d , ꢂ, ppm, J/Hz): 24.65, 27.10, 34.29,
6
49.35, 50.30, 58.77, 59.71, 101.89, 103.96, 106.13, 112.09, 112.97, 115.63, 116.58 (t, J = 259.0), 118.83, 123.56, 124.82,
CF
125.95, 131.22, 131.41, 138.74, 148.17, 149.61 (t, J = 2.7), 151.22, 162.16, 166.20, 181.49.
CF
(1R,5S)-3-{[(2Z)-6-Hydroxy-3-oxo-2-(2-chlorobenzylidene)-2,3-dihydro-1-benzofuran-7-yl]methyl}-1,2,3,4,5,6-
hexahydro-8H-1,5-methanopyrido[1,2-a][1,5]diazocin-8-one (3h). C H ClN O , yield 57%, mp 238–240ꢃÑ. MS(CI):
27 23
2 4
+
1
475.2 [M + H] (100%). Í NMR spectrum (400 MHz, DMSO-d , ꢂ, ppm, J/Hz): cytisine protons: 1.67–1.84 (2H, m, H-8),
6
2.39–2.58 (3H, m, H-9, 11à, 13à), 2.91–3.10 (3H, m, H-7, 11b, 13b), 3.65–3.83 (4H, m, H-10, N(12)-CH -Ar), 6.05 (1H, d,
2
711