C. Cimarelli, G. Palmieri / Tetrahedron: Asymmetry 11 (2000) 2555±2563
2561
Na2CO3. The aqueous solution was then extracted with CH2Cl2 (3Â30 cm3). The organic layer
was dried with anhydrous Na2SO4 then ®ltered and the solvent evaporated under reduced pressure.
Chromatographic separation on the crude oil obtained, with cyclohexane:ethyl acetate=70:30 as
eluent, aorded to the amines 3 in 45±88% yield. Products (R,R)-3a±i,m,r,t±v were identi®ed
according to literature data. Since only the major diastereomers were obtained pure by chroma-
1
tography, the H NMR signals for the minor diastereoisomers were deduced from the spectra of
the crude reaction mixtures or from enriched chromatographic fractions.
3.2. N-[(1R)-2-Ethyl-1-methylbutyl]-N-[(1R)-1-phenylethyl]amine [(R,R)-3l]
Oil, ꢀ2D0=+48.7 (c 1.79, CHCl3); NMR (CDCl3): ꢁH 0.78 (t, 3H, J=7.6 Hz), 0.83 (d, 3H,
J=6.5 Hz), 0.92 (t, 3H, J=7.6 Hz), 1.08±1.37 (m, 4H), 1.29 (d, 3H, J=6.4 Hz), 1.44±1.58 (m,
1H), 2.49 (dq, 1H, J=6.4; 4.3 Hz), 3.75 (br s, 1H), 3.83 (q, 1H, J=6.5 Hz), 7.15±7.35 (m, 5H); ꢁC
12.2, 12.6, 16.8, 21.5, 23.2, 24.5, 45.4, 51.6, 55.3, 126.5, 126.6, 128.1, 128.2; m/z 204 (M+-15, 1),
148 (58), 106 (14), 105 (100). Anal. calcd for C15H25N, MW 219.366: C, 82.13; H, 11.49; N,
6.39%. Found: C, 82.27; H, 11.32; N, 6.61%. N-[(1R)-2-Ethyl-1-methylbutyl]-N-[(1R)-1-phenyl-
ethyl]amine [(1S,aR)-3l]: NMR (CDCl3): ꢁH 0.77 (t, 3H, J=7.3 Hz), 0.82 (d, 3H, J=6.4 Hz), 0.94
(t, 3H, J=6.1 Hz), 1.08±1.37 (m, 4H), 1.28 (d, 3H, J=6.7 Hz), 1.44±1.58 (m, 1H), 2.64 (dq, 1H,
J=6.4; 3.4 Hz), 3.75 (br s, 1H), 3.85 (q, 1H, J=6.7 Hz), 7.15±7.35 (m, 5H); m/z 204 (M+-15, 1),
148 (53), 106 (12), 105 (100).
3.3. N-[(1R,2E)-1-Methyl-3-phenylprop-2-enyl]-N-[(1R)-1-phenylethyl]amine [(E)-(R,R)-3n]
Yellow oil, ꢀ2D0=+166.2 (c 1.66, CHCl3): ꢂmax (liquid ®lm) 3306, 1600, 1578, 967, 750, 700
cm^1; NMR (CDCl3): ꢁH 1.18 (d, 3H, J=6.5 Hz), 1.34 (d, 3H, J=6.7 Hz), 1.62 (br s, 1H), 3.11
(dq, 1H, J=8.1, 6.5 Hz), 3.88 (q, 1H, J=6.7 Hz), 6.27 (dd, 1H, J=16.0, 6.3 Hz), 6.27 (d, 1H,
J=16.0 Hz), 7.15±7.49 (m, 10H); ꢁC 23.2, 25.5, 53.7, 55.4, 126.7, 127.1, 127.3, 127.8, 128.9, 129.0,
130.6, 134.7, 137.7, 146.3; m/z 251 (M+, 9), 236 (20), 160 (50), 132 (59), 131(68), 105 (100). Anal.
calcd for C18H21N, MW 251.366: C, 86.01; H, 8.42; N, 5.57%. Found: C, 85.95; H, 8.23; N,
5.32%. N-[(1S,2E)-1-Methyl-3-phenylprop-2-enyl]-N-[(1R)-1-phenylethyl]amine [(1S,E),(aR)-3n]:
yellow oil, NMR (CDCl3): ꢁH 1.23 (d, 3H, J=6.5 Hz), 1.38 (d, 3H, J=7.0 Hz), 1.69 (br s, 1H),
3.36 (quint, 1H, J=4.5 Hz), 3.93 (q, 1H, J=6.6 Hz), 6.07 (dd, 1H, J=7.6, 15.9 Hz), 6.43 (d, 1H,
J=15.9 Hz), 7.17±7.42 (m, 10H); m/z 251 (M+, 12), 236 (27), 160 (39), 132 (53), 131 (64), 105
(100).
3.4. N-[(1R)-1-(3-Phenanthryl)ethyl]-N-[(1R)-1-phenylethyl]amine [(R,R)-3o]
Yellow oil, ꢀ2D0=+124.0 (c 1.61, CHCl3), ꢂmax (liquid ®lm): 3324, 1602, 1123, 841, 748, 701
cm^1; NMR (CDCl3): ꢁH 1.34 (d, 3H, J=6.7 Hz), 1.45 (d, 3H, J=6.6 Hz), 1.76 (br s, 1H), 3.58 (q,
1H, J=6.7 Hz), 3.82 (q, 1H, J=6.7 Hz), 7.24±8.00 (m, 12H), 8.47 (s, 1H), 8.72 (m, 1H); ꢁC 25.1,
25.1, 55.3, 55.6, 120.9, 122.7, 125.2, 125.4, 126.3, 126.5, 126.5, 126.6, 126.7, 126.9, 127.2, 128.5,
128.6, 128.9, 130.3, 130.3, 131.2, 132.2; m/z 310 (M+-15, 38), 206 (77), 205 (77), 120 (59), 105
(100). Anal. calcd for C24H23N, MW 325.446: C, 88.57; H, 7.12; N, 4.30%. Found: C, 88.30; H,
7.36; N, 4.22%. N-[(1S)-1-(3-Phenanthryl)ethyl]-N-[(1R)-1-phenylethyl]amine [(1S,aR)-3o]: NMR
(CDCl3): ꢁH 1.51 (d, 3H, J=6.6 Hz), 1.66 (d, 3H, J=6.4 Hz), 1.76 (br s, 1H), 3.84 (q, 1H, J=6.5
Hz), 4.09 (q, 1H, J=6.5 Hz), 7.24±8.00 (m, 12H), 8.60±8.80 (m, 2H).