141.5 (C), 131.0 (CH), 128.6 (CH), 128.2 (CH), 127.2 (CH),
126.7 (CH), 121.1 (C), 110.1 (CH), 107.8 (CH), 85.4 (CH), 63.1
(C), 38.4 (CH2), 24.5 (Me), 18.9 (CH2), 14.0 (Me); m/z (CI) 414/
412 (MHϩ, 0.1%), 245 (4), 244 (7), 242 (19), 215 (94), 213 (100),
197 (72), 196 (34), 183 (24), 133 (65), 120 (5), 107(15), 91 (15).
[α]2D6 Ϫ90.5 (c 0.74, CHCl3); (Found: MHϩ, 248.2017. C16H25NO
ϩ H requires 248.2014); νmax(film)/cmϪ1 3257, 3083, 3063, 3022,
2955, 2930, 2868, 1455, 1373, 1358, 1107, 1061, 1030, 994, 912,
758, 697; δH (300 MHz; CDCl3) 7.30 (5 H, m, ArH), 5.76 (1 H,
ddd, J 17.5, 10.3, 8.1, ᎐CH), 5.21 (3 H, m, NH, ᎐CH ), 4.55
᎐
᎐
2
(1 H, dd, J 7.7, 6.0, OCH), 3.35 (1 H, br q, J 6.7, NCH), 1.78
(1 H, m, CHH), 1.58–1.15 (7 H, m, CHH, 3 × CH2), 0.89 (3 H,
t, J 8.6, Me), 0.85 (3 H, t, J 7.1, Me); δC (75 MHz; CDCl3) 143.3
(C), 139.8 (CH), 128.3 (CH), 127.2 (CH), 126.6 (CH), 116.4
(CH2), 85.5 (CH), 64.2 (CH), 38.7 (CH2), 33.9 (CH2), 19.1
(CH2), 19.0 (CH2), 14.1 (Me), 14.0 (Me); m/z (CI) 248 (MHϩ,
53%), 236 (13), 149 (36), 133 (100), 116 (16), 107 (23), 98 (9), 91
(12).
Additions of phenyllithium
Phenyllithium was used as commercially supplied in cyclo-
hexane–ether.
(1R,1ЈS )-(؊)-N-(1-Phenylbutoxy)-2-methyl-1-phenylpropyl-
amine 3d. Obtained from the addition of phenyllithium to
(S)-O-(1-phenylbutyl)isobutyraldehyde oxime 2b as a colour-
less oil (38%, 95% de); [α]2D2 Ϫ64.9 (c 1.17, CHCl3); (Found:
MHϩ, 298.2171. C20H27NO ϩ H requires 298.2171); νmax(film)/
cmϪ1 3027, 2960, 1495, 1454, 1362, 1024, 753; δH (300 MHz;
CDCl3) 7.40–7.24 (10 H, m, ArH), 5.59 (1 H, d, J 7.7, NH), 4.34
(1 H, dd, J 5.3, 8.3, OCH), 3.72 (1 H, d, J 7.7, CH), 1.85 (1 H,
heptet, J 6.8, CH(Me)2), 1.56 (1 H, m, CHH), 1.33 (1 H, m,
CHH ), 1.09 (1 H, m, CHH), 0.90 (3 H, d, J 6.7, Me), 0.85 (1 H,
m, CHH ), 0.67 (3 H, d, J 6.7, Me), 0.67 (3 H, t, J 7.3, Me);
δC (100 MHz; CDCl3) 143.6 (C), 141.7 (C), 128.4 (CH), 128.2
(CH), 127.7 (CH), 127.1 (CH), 126.8 (CH), 126.5 (CH), 85.1
(CH), 71.9 (CH), 38.7 (CH2), 31.0 (CH), 20.0 (Me), 19.3 (Me),
18.7 (CH2), 13.8 (Me); m/z (CI) 298 (MHϩ, 34%), 166 (5), 150
(100), 133 (4), 106 (10), 72 (1).
(3R,1ЈS )-(؊)-N-(1-Phenylbutoxy)-3-hepta-1,6-dienylamine
3h. Obtained from the addition of vinyllithium to (S)-O-(1-
phenylbutyl)pent-4-enaldehyde oxime 2c as a colourless oil
(77%, 94% de); [α]2D6 Ϫ83.5 (c 0.85, CHCl3); (Found: MHϩ,
260.2012. C17H25NO ϩ H requires 260.2014); νmax(film)/cmϪ1
3257, 3078, 3027, 2955, 2925, 2863, 1690, 1644, 1598, 1501,
1450, 1358, 1301, 1199, 1107, 1061, 1030, 994, 907, 758, 697;
δH (300 MHz; CDCl3) 7.29 (5 H, m, ArH), 5.75 (2 H, m, 2 ×
᎐CH), 5.17 (2 H, m, ᎐CH ), 4.95 (2 H, m, ᎐CH ), 4.54 (1 H, dd,
᎐
᎐
᎐
2
2
J 7.5, 5.9, OCH), 3.36 (1 H, q, J 7.2, NCH), 2.02 (2 H, m, CH2),
1.77 (1 H, m, CHH), 1.60–1.19 (5 H, m, CHH, 2 × CH2), 0.89
(3 H, t, J 7.2, Me), NH signal not observed; δC (75 MHz;
CDCl3) 143.2 (C), 139.4 (CH), 138.2 (CH), 128.3 (CH), 127.3
(CH), 126.6 (CH), 116.8 (CH2), 114.7 (CH2), 85.5 (CH), 63.8
(CH), 38.7 (CH2), 30.9 (CH2), 30.0 (CH2), 19.2 (CH2), 14.1
(Me); m/z (CI) 260 (MHϩ, 95%), 215 (50), 169 (18), 128 (100).
(1R,1ЈS )-(؊)-N-(1-Phenylbutoxy)-2,2-dimethyl-1-phenyl-
propylamine 3e. Obtained from the addition of phenyllithium to
(S)-O-(1-phenylbutyl)pivaldehyde oxime 2d as a colourless
solid (31%, >98% de); mp 39–40 ЊC; [α]2D4 Ϫ67.1 (c 1.46, CHCl3);
(Found: MHϩ, 312.2322. C21H29NO ϩ H requires 312.2327);
νmax(Nujol)/cmϪ1 3027, 2955, 2863, 1449, 1362, 1050, 1004, 697;
δH (300 MHz; CDCl3) 7.45–7.28 (10 H, m, ArH), 5.74 (1 H, s,
NH), 4.41 (1 H, dd, J 5.0, 8.9, OCH), 3.82 (1 H, s, CH), 1.49
(1 H, m, CHH), 1.31 (1 H, m, CHH ), 0.86 (2 H, m, CH2), 0.86
(9 H, s, 3 × Me), 0.61 (3 H, t, J 7.4, Me); δC (100 MHz; CDCl3)
143.8 (C), 141.1 (C), 129.2 (CH), 128.2 (CH), 127.2 (CH), 127.1
(CH), 126.7 (CH), 126.5 (CH), 85.2 (CH), 74.5 (CH), 38.7
(CH2), 33.6 (C), 27.2 (Me), 18.6 (CH2), 13.7 (Me); m/z (CI) 312
(MHϩ, 1%), 254 (37), 133 (41), 121 (99), 90 (98), 76 (44).
(1S,1ЈS )-(؊)-N-(1-Phenylbutoxy)-1-cyclohexylprop-2-enyl-
amine 3i. Obtained from the addition of vinyllithium to (S)-O-
(1-phenylbutyl)cyclohexanecarboxaldehyde oxime 2f as
a
colourless oil (74%, 92% de); [α]2D7 Ϫ72.3 (c 0.83, CHCl3);
(Found: Mϩ, 287.2248. C19H29NO requires 287.2249);
νmax(film)/cmϪ1 3263, 3064, 3030, 2958, 2926, 2853, 1494, 1451,
1106, 1061, 1028, 996, 916, 760, 700; δH (300 MHz; CDCl3) 7.29
(5 H, m, ArH), 5.76 (1 H, ddd, J 17.0, 10.7, 8.7, ᎐CH), 5.28
᎐
(1 H, br s, NH) 5.13 (2 H, m, ᎐CH ), 4.53 (1 H, dd, J 7.7, 5.8,
᎐
2
OCH), 3.12 (1 H, dd, J 8.7, 6.6, NCH), 1.84–0.89 (15 H, m, CH,
7 × CH2), 0.88 (3 H, t, J 7.2, Me); δC (75 MHz; CDCl3) 143.4
(C), 138.2 (CH), 128.2 (CH), 127.2 (CH), 126.7 (CH), 117.2
(CH2), 85.3 (CH), 69.6 (CH), 39.0 (CH), 38.7 (CH2), 30.0
(CH2), 28.9 (CH2), 26.5 (CH2), 26.23 (CH2), 26.20 (CH2), 19.2
(CH2), 14.1 (Me); m/z (FI) 287 (Mϩ, 100%), 202 (21), 133 (8).
(1R,1ЈS )-(؊)-N-(1-Phenylbutoxy)-2,2-dimethyl-1-phenyl-
butylamine 3f. Obtained from the addition of phenyllithium to
(S)-O-(1-phenylbutyl)-2,2-dimethylbutyraldehyde oxime 2e as
a colourless oil (32%, >98% de); [α]2D1 Ϫ55.2 (c 1.05, CHCl3);
(Found: MHϩ, 326.2491. C22H31NO ϩ H requires 326.2484);
νmax(film)/cmϪ1 3021, 2960, 2868, 1598, 1490, 1449, 1362, 1301,
1198, 1024, 906, 697; δH (300 MHz; CDCl3) 7.39–7.26 (10 H, m,
ArH), 5.73 (1 H, s, NH), 4.40 (1 H, dd, J 4.9, 8.8, OCH), 3.89
(1 H, s, HCNH), 1.47 (1 H, m, CHH), 1.24 (1 H, m, CHH ),
1.21 (2 H, m, CH2), 0.95 (2 H, m, CH2) 0.84 (3 H, t, J 7.4, Me),
0.82 (3 H, s, Me), 0.76 (3 H, s, Me), 0.63 (3 H, t, J 7.2, Me);
δC (75 MHz; CDCl3) 143.8 (C), 140.9 (C), 129.3 (CH), 128.2
(CH), 127.1 (CH), 127.1 (CH), 126.6 (CH), 126.4 (CH), 85.1
(CH), 72.7 (CH), 38.7 (CH2), 36.2 (C), 31.9 (CH2), 23.7 (Me),
23.6 (Me), 18.6 (CH2), 13.7 (Me), 8.0 (Me); m/z (CI) 326 (MHϩ,
30%), 254 (100), 194 (15), 176 (36), 161 (65), 133 (93), 122 (75),
105 (52), 91 (25).
(3S,1ЈR)-(؉)-N-(1-Phenylbutoxy)-9-ethyl-3-deca-1,9-dienyl-
amine 3j. Obtained from the addition of vinyllithium to
(E)-(R)-O-(1-phenylbutyl)-7-ethyloct-7-enaldehyde oxime 2g as
a colourless oil (76%, >95% de); [α]2D5 ϩ72.3 (c 1.01, CHCl3);
(Found: MHϩ, 330.2792. C22H35NO ϩ H requires 330.2797);
νmax(film)/cmϪ1 3258, 3078, 3022, 2960, 2925, 2873, 2848, 1639,
1491, 1455, 1358, 1102, 1061, 1030, 989, 912, 886, 758, 697;
δH (300 MHz; CDCl3) 7.30 (5 H, m, ArH), 5.76 (1 H, ddd,
J 17.3, 10.2, 7.9, ᎐CH), 5.15 (3 H, m, NH, ᎐CH ), 4.67 (2 H, m,
᎐
᎐
2
᎐CH2), 4.54 (1 H, dd, J 7.5, 5.8, OCH), 3.33 (1 H, q, J 6.9,
᎐
NCH), 1.97 (4 H, m, 2 × CH2), 1.78 (1 H, m, CHH), 1.59–1.14
(11 H, m, CHH, 5 × CH2), 1.01 (3 H, t, J 7.4, Me), 0.89 (3 H, t,
J 7.3, Me); δC (75 MHz; CDCl3) 151.7 (C), 143.3 (C), 139.8
(CH), 128.3 (CH), 127.3 (CH), 126.6 (CH), 116.5 (CH2), 107.4
(CH2), 85.5 (CH), 64.4 (CH), 38.7 (CH2), 36.2 (CH2), 31.7
(CH2), 29.3 (CH2), 28.7 (CH2), 27.6 (CH2), 25.7 (CH2), 19.2
(CH2), 14.1 (Me), 12.4 (Me); m/z (CI) 330 (MHϩ, 100%), 198
(11), 180 (8), 133 (9).
Addition of vinyllithium
Vinyllithium was prepared in ether by transmetallation of
tetravinyltin using methyllithium according to the literature
procedure.35 The additions of vinyllithium were carried out at
Ϫ90 ЊC.
(3S,1ЈR)-(؉)-N-(1-Phenylbutoxy)-3,4-dimethyl-3-pent-1-
enylamine 3k. Obtained from the addition of vinyllithium to
(R)-3-O-(1-phenylbutyl)-3-methylbutan-2-one oxime 2i(R) as a
colourless oil (54%, >95% de); [α]2D6 ϩ117.3 (c 0.81, CHCl3);
(3R,1ЈS )-(؊)-N-(1-Phenylbutoxy)-3-hex-1-enylamine 3g.
Obtained from the addition of vinyllithium to (S)-O-(1-phenyl-
butyl)butyraldehyde oxime 2a as a colourless oil (87%, 84% de);
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2, 2 6 5 – 2 7 6
271