The Journal of Organic Chemistry
Page 18 of 29
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NMR{ H} (126 MHz, methanol-d
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, δ): 164.6, 155.7, 153.7, 148.5, 143.7, 137.8, 133.8, 126.8, 122.1, 121.4, 120.7,
]+ calcd for
3 3
19.4, 114.6, 94.3, 77.4, 51.8, 38.1, 34.2, 29.9, 14.8; HRMS (ESI/Q-TOF) m/z: [M - CH SO
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C
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H
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N
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O 374.2227; found 374.3047.
N-(1-(8-cyano-7-hydroxyquinolin-2-yl)but-3-en-1-yl)-N,N-dimethylbenzenaminium
methanesulfonate
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(16a). (14 mg, 63% yield). H NMR (500 MHz, methanol-d
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, δ): 7.88 – 7.78 (m, 3H), 7.59 (d, J = 9.3 Hz, 1H),
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.52 (dd, J = 8.6, 6.4 Hz, 2H), 7.47 (d, J = 7.1 Hz, 1H), 6.94 (d, J = 9.2 Hz, 1H), 6.83 (d, J = 8.0 Hz, 1H), 5.52 –
.40 (m, 1H), 5.24 (dd, J = 11.5, 3.1 Hz, 1H), 5.04 – 4.91 (m, 2H), 3.95 (s, 3H), 3.88 (s, 3H), 3.47 – 3.36 (m, 1H),
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.99 – 2.87 (m, 1H), 2.72 (s, 3H); C NMR{ H} (126 MHz, methanol-d , δ): 176.7, 151.9, 151.2, 146.5, 135.8,
31.6, 130.9, 129.9, 127.4, 121.1, 119.7, 119.1, 119.0, 80.8, 54.8, 51.6, 50.2, 48.1, 38.0, 33.5; HRMS (ESI/Q-
]+ calcd for C22
TOF) m/z: [M - CH
3
SO
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22 3
H N O 344.1757; found 344.1760.
N-((8-cyano-7-hydroxyquinolin-2-yl)methyl)-4-((8S,11R,13S,14S,17S)-17-hydroxy-13-methyl-3-oxo-17-
prop-1-yn-1-yl)-2,3,6,7,8,11,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-11-yl)-N,N-
(
1
dimethylbenzenaminium methanesulfonate (30). (17 mg, 49% yield). H NMR (500 MHz, methanol-d
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, δ):
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.15 (d, J = 8.3 Hz, 1H), 7.96 (d, J = 9.1 Hz, 1H), 7.79 – 7.71 (m, 2H), 7.35 (s, 1H), 7.33 – 7.25 (m, 2H), 7.19 (d,
J = 8.3 Hz, 1H), 5.74 (s, 1H), 5.45 (s, 2H), 4.47 (d, J = 7.6 Hz, 1H), 4.04 (d, J = 20.8 Hz, 6H), 3.53 (s, 1H), 2.77
– 2.68 (m, 2H), 2.67 – 2.54 (m, 2H), 2.50 – 2.30 (m, 3H), 2.25 – 2.11 (m, 3H), 2.09 – 2.03 (m, 2H), 2.01 – 1.91
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(m, 2H), 1.86 (d, J = 16.0 Hz, 4H), 1.71 (td, J = 9.2, 7.8, 4.7 Hz, 2H), 1.49 – 1.24 (m, 4H); C NMR{ H} (126
MHz, methanol-d , δ): 200.8, 171.6, 164.5, 151.8, 148.4, 145.8, 142.0, 137.6, 133.9, 129.6, 128.7, 122.0, 121.1,
19.2, 114.7, 94.2, 81.9, 81.3, 79.0, 71.7, 60.1, 56.9, 55.3, 55.0, 49.4, 46.7, 39.8, 39.0, 38.7, 38.1, 30.6, 27.3, 25.2,
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3 3 42 3 3
2.7, 19.5, 17.0, 13.1, 1.8; HRMS (ESI/Q-TOF) m/z: [M - CH SO H N O 612.3221; found
]+ calcd for C40
12.3262.
N-(1-(8-cyano-7-hydroxyquinolin-2-yl)ethyl)-4-((8S,11R,13S,14S,17S)-17-hydroxy-13-methyl-3-oxo-17-
(
prop-1-yn-1-yl)-2,3,6,7,8,11,12,13,14,15,16,17-dodecahydro-1H-cyclopenta[a]phenanthren-11-yl)-N,N-
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dimethylbenzenaminium methanesulfonate (31). (10.8 mg, 30% yield). H NMR (500 MHz, DMSO-d
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, δ):
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.54 (s, 1H), 7.67 (dd, J = 19.2, 8.5 Hz, 2H), 7.48 (t, J = 7.4 Hz, 1H), 7.24 (dt, J = 16.4, 9.0 Hz, 2H), 6.46 (dd, J
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23.6, 9.3 Hz, 1H), 6.38 (dd, J = 11.8, 7.8 Hz, 1H), 5.65 (d, J = 10.8 Hz, 1H), 5.27 (dt, J = 18.8, 6.8 Hz, 1H),
5.14 (s, 1H), 4.44 (t, J = 6.0 Hz, 1H), 3.78 (t, J = 4.7 Hz, 6H), 2.64 (td, J = 15.2, 13.1, 7.5 Hz, 3H), 2.31 (d, J =
12.0 Hz, 3H), 2.19 – 2.06 (m, 3H), 2.00 (s, 1H), 1.93 (d, J = 4.3 Hz, 2H), 1.72 (d, J = 6.7 Hz, 4H), 1.59 (s, 5H),
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1.34 – 1.17 (m, 3H), 0.89 – 0.78 (m, 1H), 0.24 (d, J = 25.8 Hz, 3H); C NMR{ H} (126 MHz, methanol-d
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, δ):
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64.5, 156.7, 148.9, 148.7, 148.4, 146.3, 137.7, 137.6, 133.7, 132.6, 128.9, 122.0, 121.7, 121.3, 121.2, 121.0,
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