M. Espinoza-Moraga et al. / Tetrahedron: Asymmetry 21 (2010) 1988–1992
1991
52.5, 109.0, 110.7, 115.0, 118.0, 119.3, 121.5, 127.5, 135.6, 136.1,
138.3. HRMS, ESI(+)-MS: m/z calcd for [C16H20N2+H]+ 241.1705,
found 241.1701.
31.5, 34.0, 42.1, 52.6, 108.5, 110.8, 118.1, 119.7, 121.7, 127.3,
127.5, 127.9, 128.1, 128.3, 128.6, 128.7, 129.4, 130.6, 135.7, 136.0.
HRMS, ESI(+)-MS: m/z calcd for [C28H42N2+H]+ m/z 407.3426, found
407.3430.
4.3.7. (S)-1-Undecyl-1,2,3,4-tetrahydro-9H-pyrido[3,4-b]indole
2g
4.3.11. (R)-1-Phenyl-1,2,3,4-tetrahydro-9H-pyrido[3,4-b]indole
Compound 2g was not previously described: ½a D20
ꢂ
¼ ꢀ48:4 (c
2k
1.0, MeOH), 74% ee by HPLC analysis (ChiralPack OD, hexane/2-
propanol/diethylamine = 80:20:0.1, 0.8 mL/min, 254 nm, minor
isomer 7.35 min, major isomer 9.9 min). 1H NMR (400 MHz, CDCl3),
d: 0.80 (3H, t, J 7.0 Hz), 1.10–1.89 (16H, m), 1.30–1.45 (2H, m),
1.59–1.69 (1H, m), 1.72–1.82 (1H, m), 2.62–2.73 (2H, m), 2.90–
3.00 (1H, m), 3.20–3.30 (1H, m), 4.00 (1H, br s), 7.03 (1H, t, J
7.0 Hz), 7.09 (1H, t, J 7.0 Hz), 7.24 (1H, d, J 7.9 Hz), 7.39 (1H, d, J
7.9 Hz), 8.00 (1H, br s, NH). 13C NMR (100 MHz, CDCl3), d: 14.1,
22.7, 25.9, 29.4, 29.7, 29.73, 29.75, 29.79, 29.9, 32.0, 34.6, 36.0,
41.7, 52.4, 108.4, 110.9, 118.1, 119.4, 121.7, 127.3, 135.0, 135.8.
HRMS, ESI(+)-MS: m/z calcd for [C22H34N2+H]+ 327.2802, found
327.2800.
½
a 2D0
ꢂ
¼ ꢀ4:0 (c 1.0, CHCl3), {lit.14 (R)-isomer, [
D = ꢀ3.9, (c 1.03,
a]
CHCl3}, 88% ee by HPLC analysis (ChiralPack OD, hexane/2-propa-
nol/diethylamine = 80:20:0.1, 1.0 mL/min, 254 nm, minor isomer
15.5 min, major isomer 19.7 min). Mp 159–160 °C. 1H NMR
(400 MHz, CDCl3), d: 2.83–2.95 (2H, m), 3.07–3.16 (1H, m), 3.33–
3.39 (1H, m), 5.17 (1H, s), 7.10–7.19 (3H, m), 7.30–7.37 (5H, m),
7.56–7.60 (1H, m), 7.66 (1H, br s). 13C NMR (100 MHz, CDCl3), d:
22.6, 42.8, 58.1, 110.2, 110.9, 118.3, 119.4, 121.8, 127.3, 128.3,
128.6, 128.9, 134.4, 136.0, 141.9. HRMS (EI): calcd for C17H16N2
m/z 248.1314, found: 248.1320.
4.3.12. (R)-1-(2-Hydroxyphenyl)-1,2,3,4-tetrahydro-9H-pyrido
[3,4-b]indole 2l
4.3.8. (R)-1-Pentadecyl-1,2,3,4-tetrahydro-9H-pyrido[3,4-
b]indole 2h
½
a 2D0
ꢂ
¼ ꢀ11:9 (c 1.0, CHCl3), 97% ee by HPLC analysis (ChiralPack
OD, hexane/2-propanol/diethylamine = 80:20:0.1, 0.8 mL/min,
254 nm, major isomer 5.7 min, minor isomer 7.5 min). Mp 189–
190 °C. FT-IR (KBr film), cmꢀ1: 3445, 1600, HRMS. 1H NMR
(400 MHz, CDCl3), d: 2.76 (1H, br s), 2.83–2.89 (1H, m), 2.90–3.23
(2H, m), 3.46–3.40 (1H, m), 5.26 (1H, s), 6.89–6.80 (2H, m), 7.05–
7.25 (5H, m), 7.42–7.50 (2H, m). ESI(+)-MS: m/z calcd for
[C17H16N2O+H]+ m/z 265.1341, found 265.1355.
Compound 2h was not previously described: ½a D20
¼ þ11:0 (c
ꢂ
1.0, MeOH), 65% ee by HPLC analysis (ChiralPack OD, hexane/2-
propanol/diethylamine = 80:20:0.1, 0.8 mL/min, 254 nm, major
isomer 6.7 min, minor isomer 13.2 min). 1H NMR (400 MHz,
CDCl3), d: 0.66 (3H, t, J 7.0 Hz), 0.96–1.17 (24H, m), 1.20–1.35
(2H, m), 1.46–1.55 (1H, m), 1.70–1.78 (1H, m), 2.48–2.60 (2H,
m), 2.77–2.87 (1H, m), 3.10–3.17 (1H, m), 3.35–3.50 (1H, m),
3.90 (1H, br s), 6.82 (1H, t, J 7.0 Hz), 6.88 (1H, t, J 7.0 Hz), 7.10
(1H, d, J 7.9 Hz), 7.20 (1H, d, J 7.9 Hz), 9.40 (1H, br s, NH). 13C
NMR (100 MHz, CDCl3), d: 14.1, 22.7, 25.9, 29.4, 29.59, 29.6, 29.7,
29.72, 29.73, 29.75, 29.78, 29.79, 29.9, 32.0, 34.6, 36.0, 41.7, 52.4,
108.4, 110.9, 118.1, 119.4, 121.7, 127.3, 135.0, 135.8. HRMS,
ESI(+)-MS: m/z calcd for [C26H42N2+H]+ 383.3426, found 383.3429.
4.3.13. (R)-1-Benzyl-1,2,3,4-tetrahydro-9H-pyrido[3,4-b]indole
(2m)
½
a 20
ꢂ
¼ ꢀ57:9 (c 1.0, MeOH), {lit.18 (S)-isomer, ee 87%,
½
a 2D0
ꢂ
¼D þ53:0, (c 0.9, acetone)}; 79% ee by HPLC analysis (ChiralCell
OD, hexane/2-propanol/diethylamine = 80:20:0.1, 0.8 mL/min,
254 nm, major isomer 10.2 min, minor isomer 16.6 min). 1H NMR
(400 MHz, CDCl3), d: 2.76–2.79 (2H, m), 3.02–3.17 (3H, m), 3.39
(1H, ddd, J 4.9, 4.9 and 12.0 Hz), 4.43 (1H, t, J 7.0 Hz), 7.10–7.14
(2H, m), 7.25 (1H, d, J 7.5 Hz), 7.32–7.40 (5H, m), 7.49 (1H, s),
7.51 (1H, d, J 7.7 Hz), 7.53 (1H, d, J 7.5 Hz). 13C NMR (100 MHz,
CDCl3), d: 22.3, 41.6, 42.5, 54.0, 109.3, 110.7, 118.1, 119.3, 121.6,
126.9, 127.3, 128.8, 129.3, 135.4, 135.5, 138.2. HRMS, ESI(+)-MS:
m/z calcd for [C18H18N2+H]+ 263.1548, found 263.1550.
4.3.9. (R)-1-(8-Heptendecyl)-1,2,3,4-tetrahydro-9H-pyrido[3,4-
b]indo 2i
Compound 2i was not previously described: ½a D20
¼ þ12:0 (c
ꢂ
1.0, MeOH), 62% ee by HPLC analysis (ChiralCell OD, hexane/2-
propanol/diethylamine = 80:20:0.1, 0.8 mL/min, 254 nm, major
isomer 4.6 min, minor isomer 6.3 min). 1H NMR (400 MHz,
CDCl3), d: 0.90 (3H, t, J 7.0 Hz), 1.20–1.41 (20H, m), 1.41–1.58
(2H, m), 1.64–1.76 (1H, m), 1.81–1.92 (1H, m), 1.93–2.02 (5H,
m), 2.72–2.78 (2H, m), 3.02–3.07 (1H, m), 3.33–3.37 (1H, m),
4.05–4.09 (1H, m), 5.29–5.40 (2H, m), 7.09–7.15 (2H, m), 7.31
(1H, d, J 8.0 Hz), 7.49 (1H, d, J 8.0 Hz), 7.92 (1H, s). 13C NMR
(100 MHz, CDCl3), d: 14.1, 22.3, 22.6, 25.8, 27.2, 27.25, 29.2,
29.3, 29.4, 29.5, 29.55, 29.7, 29.8, 29.85, 32.0, 34.9, 42.3, 52.8,
108.7, 110.8, 118.0, 119.4, 121.6, 127.3, 129.7, 130.0, 135.6,
135.70. HRMS, ESI(+)-MS: m/z calcd for [C28H44N2+H]+
409.3583, found 409.3578.
4.3.14. (R)-1-Nicotinic-1,2,3,4-tetrahydro-9H-pyrido[3,4-b]
indole 2n
½
a 2D0
ꢂ
¼ þ34:0 (c 1.0, MeOH), 75% ee by HPLC analysis (Chiral-
Pack OD, hexane/2-propanol/diethylamine = 80:20:0.1, 0.8 mL/
min, 254 nm, major isomer 4.6 min, minor isomer 8.9 min). 1H
and 13C NMR data are in accordance with Misztal et al.19 HRMS,
ESI(+)-MS: m/z calcd for [C16H15N3+H]+ 250.1344, found 250.1338.
Acknowledgments
FONDECYT (Project 1085308) is great acknowledged for finan-
cial support to Laboratory of Asymmetric Synthesis (LAS). M.E.M.
thanks Programa de Doctorado en Productos Bioactivos-UTalca
for fellowship.
4.3.10. (R)-1-(8,11-Heptendecyl)-1,2,3,4-tetrahydro-9H-
pyrido[3,4-b]indole 2j
Compound 2j was not previously described: ½a D20
¼ þ21:6 (c 1.0,
ꢂ
MeOH), 64% ee by HPLC analysis (ChiralPack OD, hexane/2-propa-
nol/diethylamine = 80:20:0.1, 0.8 mL/min, 254 nm, major isomer
4.5 min, minor isomer 5.5 min). 1H NMR (400 MHz, CDCl3), d: 0.88
(3H, t, J 7.0 Hz), 1.26–1.35 (6H, m), 1.52–1.66 (2H, m), 1.71–1.79
(1H, m), 1.86–1.94 (1H, m), 2.03–2.16 (5H, m), 2.75–2.88 (8H, m),
3.05–3.12 (1H, m), 3.34– 3.39 (1H, m), 4.18 (1H, br s), 5.31–5.39
(8H, m), 7.07–7.14 (2H, m), 7.31 (1H, d, J 8.0 Hz), 7.47 (1H, d, J
8.0 Hz), 7.48 (1H, d, J 8.0 Hz), 7.93 (1H, br s). 13C NMR (100 MHz,
CDCl3), d: 14.1, 21.8, 22.7, 25.6, 25.7, 25.75, 25.76, 27.1, 27.2, 29.5,
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