´
J. Scianowski et al. / Tetrahedron: Asymmetry 24 (2013) 1089–1096
1095
(CH3), 25.7 (CH3), 26.5 (CH2), 27.4 (CH2), 27.9 (CH), 31.2 (CH), 35.3
(CH2), 39.7 (CH2), 42.4 (CH2), 44.5 (CH), 49.4 (CH), 121.5 (CH),
124.1 (CH), 131.5 (C), 137.8 (C) ppm; 77Se (38.1 MHz, CDCl3),
d = 189.16 ppm. Elemental Anal. Calcd for C20H36Se (355.46): C,
67.58; H, 10.21. Found: C, 67.34; H, 10.33.
(CH)G, 121.8 (CH)N, 124.0 (CH)G, 124.0 (CH)N, 131.5 (C)G, 131.8
(C)N, 137.8 (C)G, 137.9 (C)N ppm; 77Se (38.1 MHz, CDCl3),
d = 357.75G, 358.76N ppm.
4.6.6. (1S,2R,5S)-(ꢀ)-Geranyl myrtanyl selenide 49
Yield 45%; colorless liquid; ½a D20
ꢃ
¼ ꢀ114:05 (c 1.61, CHCl3); 1H
4.6.2. (1R,2S,5R)-(ꢀ)-Geranyl menthyl selenide 29
NMR (200 MHz, CDCl3), d = 0.87 (d, 2H, J = 9.0 Hz), 0.99 (s, 3H,
CH3), 1.18 (s, 3H, CH3), 1.58 (s, 3H, CH3), 1.63 (s, 3H, CH3), 1.67
(s, 3H, CH3), 1.74–2.45 (m, 11H), 2.49–2.73 (m, 2H), 3.18 (d, 2H,
CH2, J = 8.4 Hz), 5.03–5.18 (m, 1H), 5.34 (t, 1H, J = 9.6 Hz) ppm;
13C NMR (50.3 Hz, CDCl3), d = 15.8 (CH3), 17.6 (CH3), 20.6 (CH2),
23.0 (CH2), 23.2 (CH3), 25.6 (CH3), 26.1 (CH2), 26.5 (CH2), 28.0
(CH3), 31.3 (CH2), 31.7 (CH2), 33.4 (CH2), 38.6 (C), 41.3 (CH), 42.0
(CH), 46.4 (CH), 121.4 (CH), 124.0 (CH), 131.5 (C), 137.8 (C) ppm;
77Se (38.1 MHz, CDCl3), d = 185.71 ppm. Elemental Anal. Calcd for
Yield 47%; colorless liquid; ½a D20
ꢃ
¼ ꢀ81:9 (c 1.83, CHCl3); 1H
NMR (300 MHz, CDCl3), d = 0.74 (d, 3H, CH3, J = 6.9 Hz), 0.82–0.87
(m, 1H), 0.88 (d, 3H, CH3, J = 6.3 Hz), 0.90 (d, 3H, CH3, J = 6.9 Hz),
0.96–1.09 (m, 2H), 1.19–1.39 (m, 4H), 1.59 (s, 3H, CH3), 1.66 (s,
3H, CH3), 1.68 (s, 3H, CH3), 2.00–2.33 (m, 6H), 2.70 (ddd, 1H,
J = 3.9, 11.5, 11.5 Hz), 3.22 (ddd, 2H, J = 8.7, 11.8, 30.5 Hz), 5.05–
5.12 (m, 1H), 5.35 (t, 1H, J = 8.0 Hz) ppm; 13C NMR (50.3 Hz, CDCl3),
d = 15.1 (CH3), 15.9 (CH3), 17.7 (CH3), 19.2 (CH2), 21.5 (CH3), 22.2
(CH3), 25.0 (CH2), 25.7 (CH3), 26.6 (CH2), 29.0 (CH), 34.4 (CH),
34.9 (CH2), 39.7 (CH2), 43.4 (CH), 45.5 (CH2), 47.5 (CH), 121.4
(CH), 124.1 (CH), 131.6 (C), 137.7 (C) ppm; 77Se (38.1 MHz, CDCl3),
d = 269.41 ppm. Elemental Anal. Calcd for C20H36Se (355.46): C,
67.58; H, 10.21. Found: C, 67.42; H, 10.29.
C20H34Se (353.44): C, 67.97; H, 9.70. Found: C, 68.05; H, 9.58.
4.7. Neryl terpenyl selenides
4.7.1. (1S,2S,5R)-(+)-Neomenthyl neryl selenide 26
Yield 72%; colorless liquid; ½a D20
ꢃ
¼ þ48:0 (c 1.88, CHCl3); 1H
4.6.3. (1S,3R,4R,6R)-(ꢀ)-Isocaranyl geranyl selenide 37
NMR (200 MHz, CDCl3), d = 0.89 (d, 6H, 2 ꢁ CH3, J = 6.4 Hz), 0.90
(d, 3H, CH3, J = 6.6 Hz), 0.97–1.15 (m, 1H), 1.16–1.28 (m, 2H),
1.48–1.58 (m, 4H), 1.61 (s, 3H, CH3), 1.68 (s, 3H, CH3), 1.71 (s,
3H, CH3), 1.82–2.18 (m, 6H), 3.05–3.35 (m, 3H), 5.15–5.24 (m,
1H), 5.65 (t, 1H, J = 8.8 Hz) ppm; 13C NMR (50.3 MHz, CDCl3),
d = 17.7 (CH3), 20.6 (CH3), 20.7 (CH2), 21.0 (CH3), 22.2 (CH3), 23.3
(CH3), 25.7 (CH3), 26.7 (CH2), 27.4 (CH2), 27.9 (CH), 31.2 (CH),
31.7 (CH2), 35.4 (CH2), 42.5 (CH2), 45.0 (CH), 49.5 (CH), 122.3
(CH), 124.1 (CH), 131.8 (C), 137.9 (C) ppm; 77Se (38.1 MHz, CDCl3),
d = 193.09 ppm. Elemental Anal. Calcd for C20H36Se (355.46): C,
67.58; H, 10.21. Found: C, 67.79; H, 10.08.
Yield 43%; colorless liquid; ½a D20
ꢃ
¼ ꢀ69:3 (c 1.88, CHCl3); 1H
NMR (200 MHz, CDCl3), d = 0.93 (s, 3H, CH3), 0.96 (s, 3H, CH3),
1.02 (d, 2H, CH2, J = 6.4 Hz), 1.11–1.56 (m, 3H), 1.59 (s, 3H, CH3),
1.65 (s, 3H, CH3), 1.68 (s, 3H, CH3),1.92–2.14 (m, 8H), 2.17–2.35
(m, 2H), 3.18 (d, 2H, CH2, J = 8.0 Hz), 5.04–5.11 (m, 1H), 5.34 (t,
1H, J = 6.0 Hz) ppm; 13C NMR (50.3 Hz, CDCl3), d = 15.6 (CH3),
17.5 (CH3), 17.6 (C), 20.3 (CH2), 20.7 (CH), 20.8 (CH), 21.8 (CH3),
23.5 (CH3), 25.7 (CH3), 26.6 (CH2), 28.8 (CH3), 29.6 (CH2), 30.2
(CH2), 34.9 (CH), 39.6 (CH2), 44.1 (CH), 121.4 (CH), 124.1 (CH),
131.6 (C), 137.8 (C) ppm;77Se (CDCl3), d = 295.77 ppm. Elemental
Anal. Calcd for C20H34Se (353.44): C, 67.97; H, 9.70. Found: C,
68.11; H, 9.61.
4.7.2. (1R,2S,5R)-(ꢀ)-Menthyl neryl selenide 30
Yield 60%; colorless liquid; ½a D20
ꢃ
¼ ꢀ63:0 (c 1.95, CHCl3); 1H
4.6.4. (1S,2S,3R,5R)-(ꢀ)-Geranyl pinocamphyl selenide 41
NMR (300 MHz, CDCl3), d = 0.73 (d, 3H, CH3, J = 6.9 Hz), 0.80–0.86
(m, 1H), 0.88 (d, 3H, CH3, J = 6.0 Hz), 0.89 (d, 3H, CH3, J = 6.9 Hz),
0.95–1.09 (m, 2H), 1.18–1.37 (m, 4H), 1.59 (s, 3H, CH3), 1.66 (s,
3H, CH3), 1.70 (s, 3H, CH3), 2.07–2.34 (m, 6H), 2.67–2.71 (m, 1H),
3.17–3.24 (m, 2H), 5.12–5.25 (m, 1H), 5.37 (t, 1H, J = 8.0 Hz)
ppm; 13C NMR (50.3 Hz, CDCl3), d = 15.1 (CH3), 17.7 (CH3), 19.0
(CH3), 21.5 (CH2), 22.2 (CH3), 23.4 (CH3), 25.0 (CH2), 25.7 (CH3),
26.7 (CH2), 29.0 (CH), 31.8 (CH), 34.4 (CH2), 34.9 (CH2), 43.7 (CH),
45.5 (CH2), 47.6 (CH), 122.0 (CH), 124.1 (CH), 131.8 (C), 138.0 (C)
ppm; 77Se (38.1 MHz, CDCl3), d = 273.98 ppm. Elemental Anal.
Calcd for C20H36Se (355.46): C, 67.58; H, 10.21. Found: C, 67.64;
H, 10.16.
Yield 44%; colorless liquid; ½a D20
ꢃ
¼ ꢀ23:0 (c 1.57, CHCl3); 1H
NMR (200 MHz, CDCl3), d = 1.01 (s, 3H, CH3), 1.18 (s, 3H, CH3),
1.21 (d, 3H, CH3, J = 6.4 Hz), 1.32-.1.37 (m, 1H), 1.62 (s, 3H, CH3),
1.69 (s, 3H, CH3), 1.70 (s, 3H, CH3), 1.82–2.00 (m, 2H), 2.00–2.65
(m, 8H), 3.23 (d, 2H, CH2, J = 8.0 Hz), 3.69–8.82 (m, 1H), 5.03–
5.16 (m, 1H), 5.38 (t, 1H, J = 6.8 Hz) ppm; 13C NMR (50.3, CDCl3),
d = 15.9 (CH3), 17.7 (CH3), 19.8 (CH3), 20.7 (CH2), 23.5 (CH3), 25.7
(CH3), 26.6 (CH2), 27.6 (CH3), 28.1 (CH2), 33.0 (CH), 36.6 (CH2),
38.3 (CH), 39.5 (CH2), 39.7 (C), 42.0 (CH), 49.0 (CH), 121.4 (CH),
124.0 (CH), 131.6 (C), 138.0 (C) ppm. 77Se (38.1 MHz, CDCl3),
d = 252.74 ppm. Elemental Anal. Calcd for C20H34Se (353.44): C,
67.97; H, 9.70. Found: C, 67.69; H, 9.76.
4.7.3. (1S,3R,4R,6R)-(ꢀ)-Isocaranyl neryl selenide 38
4.6.5. (1S,2S,3S,5R)-(ꢀ)-Geranyl isopinocamphyl selenide 45
Yield 51%; mixture 74%: 26%; 1H NMR (200 MHz, CDCl3),
d = 1.02 (s, 3H, CH3)G, 1.02 (s, 3H, CH3)N, 1.12 (d, 3H, CH3,
J = 7.0 Hz)G, 1.12 (d, 3H, CH3, J = 7.0 Hz)N, 1.19 (s, 3H, CH3)G, 1.19
(s, 3H, CH3)N, 1.60 (s, 3H, CH3)G, 1.62 (s, 3H, CH3)N, 1.68 (s, 3H,
CH3)G, 1.69 (s, 3H, CH3)G, 1.69 (s, 3H, CH3)N, 1.73 (s, 3H, CH3)N,
1.78–1.98 (m, 3H)G, 1.78–1.98 (m, 3H)N, 2.05–2.09 (m, 5H)G,
2.05–2.09 (m, 5H)N, 2.17–2.70 (m, 3H)G, 2.17–2.70 (m, 3H)N,
3.01–3.37 (m, 3H)G, 3.01–3.37 (m, 3H)N, 5.05–5.22 (m, 1H)G,
5.05–5.22 (m, 1H)N, 5.38 (t, 1H, J = 7.8 Hz)G, 5.39 (t, 1H,
J = 8.0 Hz)N ppm; 13C NMR (50.3, CDCl3), d = 15.8 (CH3)G,17.6
(CH3)G, 17.7 (CH3)N, 20.6 (CH2)N, 20.8 (CH2)G, 21.3 (CH3)G, 21.3
(CH3)N, 23.2 (CH3)G, 23.2 (CH3)N, 23.4 (CH3)N, 25.6 (CH3)G, 25.7
(CH3)N, 26.6 (CH2)G, 26.7 (CH2)N, 27.9 (CH3)G, 27.9 (CH3)N, 31.7
(CH2)N, 34.0 (CH2)N, 34.1 (CH2)G, 36.5 (CH)G, 36.9 (CH)N, 38.6
(C)N, 38.7 (CH2)G, 38.7 (CH2)N, 38.9 (C)G, 39.6 (CH2)G, 42.5 (CH)G,
42.5 (CH)N, 45.4 (CH)G, 45.5 (CH)N, 48.4 (CH)G, 48.4 (CH)N, 121.3
Yield 61%; colorless liquid; ½a D20
ꢃ
¼ ꢀ89:4 (c 0.94, CHCl3); 1H
NMR (200 MHz, CDCl3), d = 0.93 (s, 3H, CH3), 0.95 (s, 3H, CH3),
1.01 (d, 2H, CH2, J = 6.4 Hz), 1.16–1.56 (m, 3H), 1.61 (s, 3H, CH3),
1.69 (s, 3H, CH3), 1.71 (s, 3H, CH3),1.92–2.15 (m,8H), 2.19–2.37
(m, 2H), 3.18 (d, 2H, CH2, J = 8.0 Hz), 5.05–5.21 (m, 1H), 5.34 (t,
1H, J = 6.0 Hz) ppm; 13C NMR (50.3 Hz, CDCl3), d = 15.6 (CH3),
17.5 (C), 17.7 (CH3), 20.1 (CH2), 20.7 (CH), 20.8 (CH), 21.8 (CH3),
23.4 (CH3), 25.7 (CH3), 26.7 (CH2), 28.9 (CH3), 29.6 (CH2), 30.2
(CH2), 31.8 (CH2), 34.9 (CH), 44.5 (CH), 121.2 (CH), 124.1 (CH),
131.8 (C), 138.0 (C) ppm;77Se (CDCl3), d = 296.74 ppm. Elemental
Anal. Calcd for C20H34Se (353.44): C, 67.97; H, 9.70. Found: C,
68.09; H, 9.64.
4.7.4. (1S,2S,3R,5R)-(ꢀ)-Neryl pinocamphyl selenide 42
Yield 57%; mixture 64%: 36% 1H NMR (200 MHz, CDCl3), d = 1.01
(s, 3H, CH3)G, 1.02 (s, 3H, CH3)N, 1.18 (s, 3H, CH3)G, 1.19 (s, 3H,
CH3)N, 1.21 (d, 3H, CH3, J = 6.4 Hz)G, 1.22 (d, 3H, CH3, J = 6.4 Hz)N,