Issue in Honor of Prof. Michael Orfanopoulos
ARKIVOC 2015 (iii) 154-166
(2H, q, J 7.1 Hz), 4.72 (2H, s), 4.94 (1H, brs), 7.20 (2H, d, J 7.0 Hz), 7.24 (1H, t, J 7.4 Hz), 7.31 (2H, dd, J 7.0, 7.4 Hz). 13C NMR (125 MHz, CDCl3): δC 14.1, 22.4, 30.7, 36.7, 43.3, 60.7, 98.4, 126.7 (2C), 127.4, 128.7 (2C), 137.4, 144.1, 172.0, 178.0. HRMS (TOF ESI): calcd for C16H20NO3: 274.1438 [M+H]+; found: 274.1438. Ethyl 3-(3-oxo-2,3,5,6,11,11b-hexahydro-1H-indolizino[8,7-b]indol-11b-yl)propanoate 22 (4a). Isolated yield 58%. 1H NMR (500 MHz, CDCl3): δH 1.23 (3H, t, J 7.2 Hz), 2.19-2.40 (5H, m), 2.41-2.50 (2H, m), 2.63-2.70 (1H, m), 2.74-2.89 (2H, m), 3.08-3.16 (1H, m), 4.05-4.15 (2H, m), 4.50 (1H, dd, J 5.9, 13.2 Hz), 7.12 (1H, t, J 7.2 Hz), 7.19 (1H, t, J 7.2 Hz), 7.33 (1H, d, J 8.0 Hz), 7.47 (1H, d, J 7.8 Hz), 8.42 (1H, brs). 13C NMR (125 MHz, CDCl3): δC 14.1, 20.8, 29.8, 30.7, 30.8, 34.7, 35.8, 61.0, 62.0, 107.7, 111.0, 118.5, 119.8, 122.3, 126.5, 135.9, 136.1, 173.0, 173.9. HRMS (TOF ESI): calcd for C19H22N2NaO3: 349.1523 [M + Na]+; found: 349.1520. 11b-Methyl-5,6,11,11b-tetrahydro-1H-indolizino[8,7-b]indol-3(2H)-one (4b).22 Isolated yield 45%. 1H NMR (500 MHz, CDCl3): δH 1.59 (3H, s), 2.13-2.20 (1H, m), 2.27-2.32 (1H, m), 2.46 (1H, ddd, J 1.8, 9.6, 11.4 Hz), 2.63-2.71 (1H, m), 2.75-2.88 (2H, m), 3.09 (1H, td, J 5.5, 11.9 Hz), 4.46 (1H, dd, J 5.1, 13.0 Hz), 7.10 (1H, dd, J 7.1, 7.8 Hz), 7.16 (1H, ddd, J 1.0, 7.1, 8.0 Hz), 7.33 (1H, d, J 8.0 Hz), 7.46 (1H, d, J 7.8 Hz), 8.64 (1H, brs). 13C NMR (125 MHz, CDCl3): δC 21.1, 25.3, 30.7, 32.8, 34.9, 59.5, 106.6, 111.0, 118.4, 119.6, 122.0, 126.6, 136.1, 137.8, 172.8 ppm. HRMS (TOF ESI): calcd for C15H17N2O: 241.1335 [M + H]+; found: 241.1337. 1,11b-Dimethyl-5,6,11,11b-tetrahydro-1H-indolizino[8,7-b]indol-3(2H)-one (4c).22 Isolated in 51% yield as a 6:4 cis/trans mixture of inseparable diastereomers. The fact that the cis compound is the major one in the isolated mixture of the two diastereoisomers was confirmed by comparison with the known in the literature38 β-carboline (cis diastereoisomer). 1H NMR (500 MHz, CDCl3): δH 0.74 (3H of trans, d, J 7.0 Hz), 1.36 (3H of cis, d, J 6.6 Hz), 1.45 (3H of cis, s), 1.58 (3H of trans, s), 2.10 (1H of trans, d, J 16.5 Hz), 2.31-2.35 (1H of cis, m), 2.44-2.57 (2H of cis plus 1H of trans, m), 2.74-2.87 (2H of cis plus 2H of trans, m), 2.92-3.06 (1H of cis plus 1H of trans, m), 4.44-4.52 (1H of cis plus 1H of trans, m), 7.13 (1H of cis plus 1H of trans, dd, J 7.2, 7.7 Hz), 7.16-7.22 (1H of cis plus 1H of trans, m), 7.35 (1H of trans, d, J 8.0 Hz), 7.36 (1H of cis, d, J 8.0 Hz), 7.49 (1H of cis, d, J 7.7 Hz), 7.50 (1H of trans, d, J 7.7 Hz), 8.10 (1H of cis, brs), 8.24 (1H of trans, brs). 13C NMR (125 MHz, CDCl3): δC 14.8 (cis), 17.4 (trans), 19.3 (cis), 21.3 (trans), 21.4 (cis), 25.1 (trans), 34.9 (cis), 35.2 (trans), 37.9 (trans), 38.7 (cis), 39.1 (cis), 39.4 (trans), 61.6 (cis), 63.4 (trans), 107.1 (cis), 109.3 (trans), 110.9 (trans), 111.0 (cis), 118.4 (trans), 118.5 (cis), 119.7 (trans), 119.9 (cis), 122.1 (trans), 122.2 (cis), 126.6 (cis plus trans), 134.7 (trans), 136.0 (trans), 136.1 (cis), 137.8 (cis), 171.9 (cis), 172.1 (trans). HRMS (TOF ESI): calcd for C16H19N2O: 255.1492 [M + H]+; found: 255.1491. 11b-(3-Iodopropyl)-5,6,11,11b-tetrahydro-1H-indolizino[8,7-b]indol-3(2H)-one (4d). Isolated yield 55%. 1H NMR (500 MHz, CDCl3): δH 1.82-1.90 (1H, m), 1.90-2.00 (1H, m), 2.012.14 (2H, m), 2.21-2.27 (1H, m), 2.34-2.40 (1H, m), 2.48 (1H, ddd, J 2.5, 10.2, 17.0 Hz), 2.622.71 (1H, m), 2.80 (1H, dd, J 5.0, 15.4 Hz), 2.82-2.92 (1H, m), 3.14 (2H, t, J 6.6 Hz), 3.11-3.19 (1H, m), 4.53 (1H, dd, J 5.8, 13.2 Hz), 7.12 (1H, t, J 7.4 Hz), 7.19 (1H, dd, J 8.1, 7.1 Hz), 7.34 (1H, d, J 8.1 Hz), 7.48 (1H, d, J 7.8 Hz), 8.63 (1H, brs). 13C NMR (125 MHz, CDCl3): δC 6.1,
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