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J. Scianowski et al. / Tetrahedron: Asymmetry xxx (2016) xxx–xxx
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4.9.2. (8-Phenyl menthyl)-(2-methoxy-2-phenyl ethyl)selenide
43
4.9.5. (10-Naphthyl pinocamphyl)-(2-methoxy-2-phenyl ethyl)
selenide 50
Yield: 15%; dr 56:46; 1H NMR (300.0 MHz, CDCl3) d ppm: major
Yield: 31%; dr 34:66; 1H NMR (200 MHz, CDCl3): major
diastereomer d = 1.02–1.16 (m, 1H), 1.18 (s, 3H, CH3), 1.31 (s, 3H,
CH3), 1.78–1.97 (m, 2H), 1.98–2.12 (m, 1H), 2.15–2.29 (m, 1H),
2.32–2.57 (m, 1H), 2.62–2.83 (m, 1H), 2.84–2.99 (m, 1H), 3.09–
3.30 (m, 2H), 3.31 (s, 3H, CH3), 3.64–3.98 (m, 2H), 4.40–4.54 (m,
1H), 7.19–7.58 (m, 9H), 7.68–7.73 (d, 1H, J = 12.3 Hz), 7.82–7.87
(m, 1H), 8.08–8.15 (m, 1H); minor diastereomer—only separated
signals; 13C NMR (75.5 MHz, CDCl3): major diastereomer d = 24.3
(CH3), 27.3 (CH3), 27.8 (CH2), 31.1 (CH2), 34.0 (CH), 36.0 (CH2),
37.0 (CH2), 39.1 (C), 41.9 (CH), 43.9 (CH), 44.3 (CH), 57.0 (CH3),
84.4 (CH), 124.4 (CH), 125.2 (CH), 125.6 (CH), 126.5 (CH), 126.7
(2ÂCH), 126.8 (CH), 128.0 (CH), 128.5 (CH), 128.6 (2ÂCH), 128.7
(CH), 131.9 (C), 134.0 (C), 138.2 (C), 141.4 (C); minor diastere-
omer—only separated signals d = 30.886 (CH2), 33.8 (CH), 37.02
(CH2), 44.26 (CH), 56.9 (CH3), 84.3 (CH), 125.3 (CH), 127.8 (CH);
77Se NMR (38.1 MHz, CDCl3): major diastereomer d = 215.7 (Se);
minor diastereomer d = 216.4 (Se) ppm. Elemental analysis calcd
for C29H34OSe (477.54): C, 72.94; H, 7.18; found: C, 72.75; H, 7.12.
diastereomer: 0.86 (d, J = 6.3 Hz, 3H, CH3), 0.9–1.05 (m, 1H), 1.19
(s, 3H, CH3), 1.49 (s, 3H, CH3), 1.6–2.2 (m, 4H), 2.3–2.45 (m, 1H),
2.5–2.6 (m, 1H), 2.65–2.79 (m, 1H), 3.18 (s, 3H, CH3), 4.05–4.15
(m, 1H), 7.3–7.8 (m, 10H) minor diastereomer—only separated sig-
nals: 0.82 (d, J = 6.0 Hz, 3H, CH3), 1.53 (s, 3H, CH3), 1.37 (s, 3H, CH3),
3.17 (s, 3H, CH3); 13C NMR (50.3 MHz, CDCl3) d major diastere-
omer: 22.0 (CH3), 23.3 (CH3), 29.3 (CH2), 29.6 (CH2), 29.9 (CH3),
33.9 (CH), 35.2 (CH2), 40.9 (C), 41.0 (C), 41.6 (CH), 45.7 (CH2),
50.7 (CH), 56.8 (CH3), 84.8 (CH), 125.3 (CH), 126.1 (2ÂCH), 126.6
(CH), 126.9 (CH), 127.7 (2ÂCH), 128.3 (2ÂCH), 141.7 (C), 151.8
(C) minor diastereomer—only separated signals: 21.9 (CH3), 23.6
(CH3), 29.31 (CH2), 29.7 (CH3), 30.0 (CH2), 33.8 (CH), 35.1 (CH2),
40.8 (C), 41.7 (CH), 45.3 (CH2), 50.9 (CH), 56.7 (CH3), 84.1 (CH),
125.4 (CH), 141.5 (C), 151.7 (C); 77Se NMR (38.1 MHz, CDCl3) d
ppm: minor diastereomer: 258.4, major diastereomer 272.1 ppm.
Elemental analysis calcd for C25H34OSe (429.50): C, 69.91; H,
7.98; found: C, 69.87; H, 7.94.
4.9.3. (10-Phenyl pinocamphyl)-(2-methoxy-2-phenyl ethyl)
selenide 48
4.9.6. (10-Naphthyl isopinocamphyl)-(2-methoxy-2-phenyl
ethyl)selenide 51
Yield: 47 %; dr 47:53; 1H NMR (300 MHz, CDCl3): major
diastereomer d = 1.14 (s, 3H, CH3), 1.17 (s, 3H, CH3), 1.27–1.37
(m, 1H), 1.80–1.91 (m, 2H), 2.05–2.18 (m, 2H), 2.29–2.44 (m,
1H), 2.51–2.63 (m, 1H), 2.81 (ddd, 1H, J = 1.5, 5.4, 12.0 Hz), 2.88
(d, 1H, J = 12.3 Hz), 3.04 (ddd, 1H, J = 5.0, 8.1, 12.1 Hz), 3.14 (dt,
1H, J = 4.8, 13.8 Hz), 3.283 (s, 3H, CH3), 3.71–3.83 (m, 1H), 4.41
(ddd, 1H, J = 8.1 Hz, J = 5.0 Hz, J = 1.8 Hz), 7.10–7.43 (m, 10H);
minor diastereomer—only separated signals d = 3.280 (s, 3H,
CH3); 13C NMR (75.5 MHz, CDCl3): major diastereomer d = 24.065
(CH3), 27.3 (CH3), 27.6 (CH2), 30.9 (CH2), 34.0 (CH), 36.6 (CH2),
39.0 (CH2), 39.2 (C), 41.8 (CH), 43.8 (CH), 45.7 (CH), 56.9 (CH3),
84.0 (CH), 125.5 (CH), 126.7 (2ÂCH), 128.0 (CH), 128.1 (2ÂCH),
128.5 (2ÂCH), 129.2 (2ÂCH), 141.3 (C), 142.3 (C); minor diastere-
omer- only separated signals d = 31.0 (CH2), 33.8 (CH), 36.5 (CH2),
39.1 (CH2), 39.14 (C), 41.82 (CH), 43.7 (CH), 45.6 (CH), 84.4 (CH),
125.49 (CH), 126.6 (2ÂCH), 127.9 (CH), 128.5 (2ÂCH), 141.4 (C),
142.28 (C); 77Se NMR (38.1 MHz, CDCl3): major diastereomer
d = 211.0 (Se); minor diastereomer d = 210.6 (Se) ppm. Elemental
analysis calcd for C25H32OSe (427.48): C, 70.24; H, 7.55; found: C,
69.90; H, 7.58.
Yield: 43%; dr 51:49; 1H NMR (300 MHz, CDCl3): major
diastereomer d = 0.78–0.95 (m, 1H), 1.16 (s, 3H, CH3), 1.24 (s, 3H,
CH3), 1.72–1.81 (m, 1H), 1.87–1.96 (m, 1H), 2.14–2.32 (m, 3H),
2.47–2.66 (m, 1H), 2.79–3.16 (m, 3H), 3.29 (s, 3H, CH3), 3.56
(ddd, 1H, J = 3.3, 13.5, Hz), 4.44–4.51 (m, 1H), 7.15–7.57 (m, 9H),
7.68–7.73 (d, 1H, J = 12 Hz), 7.82–7.88 (m, 1H), 8.23–8.33 (m,
1H); minor diastereomer—only separated signals d = 1.13 (s, 3H,
CH3), 1.19 (s, 3H, CH3), 3.32 (s, 3H, CH3); 13C NMR (50.3 MHz,
CDCl3): major diastereomer d = 23.6 (CH3), 27.9 CH3), 30.5 (CH2),
33.8 (CH2), 36.8 (CH), 38.0 (CH2), 38.7 (CH2), 38.8 (C), 42.6 (CH),
43.5 (CH), 50.9 (CH), 57.0 (CH3), 84.7 (CH), 124.5 (CH), 125.4
(CH), 125.7 (CH), 126.6 (2ÂCH), 127.0 (CH), 127.8 (CH), 127.9
(CH), 127.9 (CH), 128.1 (CH), 128.5 (2ÂCH), 132.2 (C), 133.9 (C),
136.8 (C), 141.4 (C); minor diastereomer—only separated signals
d = 23.7 (CH3), 29.9 (CH2), 33.6 (CH2), 36.3 (CH), 38.2 (CH2), 43.4
(CH), 50.7 (CH), 56.9 (CH3), 84.6 (CH), 125.1 (CH), 141.3 (C); 77Se
NMR (38.1 MHz, CDCl3): major diastereomer d = 306.1 (Se); minor
diastereomer d = 301.7 (Se) ppm. Elemental analysis calcd for
C29H34OSe (477.54): C, 72.94; H, 7.18; found: C, 72.82; H, 6.70.
4.9.7. (2-Phenyl apopinocamphyl)-(2-methoxy-2-phenyl ethyl)
selenide 47
4.9.4. (10-Phenyl isopinocamphyl)-(2-methoxy-2-phenyl ethyl)
selenide 49
Yield: 29%; dr 43:57; 1H NMR (300 MHz, CDCl3): major
diastereomer d = 0.83–1.03 (m, 2H), 1.07 (s, 3H, CH3), 1.26 (s, 3H,
CH3), 1.37–1.42 (m, 1H), 1.92–2.03 (m, 1H), 2.27–2.57 (m, 3H),
2.65–2.73 (m, 1H), 2.48 (dt, 1H, J = 8.4, 12.3 Hz), 3.20 (s, 3H,
CH3), 3.67–3.87 (m, 1H), 4.25–4.33 (dt, 1H, J = 5.2, 8.1 Hz), 7.16–
7.39 (m, 10H); minor diastereomer—only separated signals
d = 1.08 (s, 3H, CH3), 1.29 (s, 3H, CH3), 3.21 (s, 3H, CH3); 13C NMR
(50.3 MHz, CDCl3): major diastereomer d = 25.1 (CH3), 27.7 (CH3),
30.3 (CH2), 31.5 (CH), 31.6 (CH2), 36.9 (CH2), 38.5 (C), 42.2 (CH),
47.8 (CH), 49.7 (CH), 56.8 (CH3), 84.2 (CH), 125.9 (CH), 126.8
(2ÂCH), 126.9 (2ÂCH), 127.9 (CH), 128.4 (2ÂCH), 130.3 (2ÂCH),
141.5 (C), 143.2 (C); minor diastereomer—only separated signals
d = 25.2 (CH3), 30.33 (CH2), 31.6 (CH2), 37.0 (CH2), 42.3 (CH), 47.7
(CH), 49.6 (CH), 56.9 (CH3), 84.6 (CH), 126.6 (CH), 126.8 (2ÂCH),
127.8 (CH), 141.6 (C); 77Se NMR (38.1 MHz, CDCl3): major diastere-
omer d = 258.9 (Se); minor diastereomer d = 263.9 (Se) ppm. Ele-
mental analysis calcd for C24H30OSe (413.45): C, 69.72; H, 7.31;
found: C, 70.07; H, 7.27.
Yield: 41%; dr 56:44; 1H NMR (200 MHz, CDCl3): major
diastereomer d = 0.81–0.99 (m, 2H), 1.11 (s, 3H, CH3), 1.17 (s,
3H, CH3), 1.68–1.85 (m, 1H), 1.85–1.98 (m, 1H), 2.12–2.33 (m,
3H), 2.38–2.64 (m, 2H), 2.79–3.22 (m, 3H), 2.29 (s, 3H, CH3),
4.30–4.51 (m, 1H), 7.04–7.42 (m, 10H); minor diastereomer- only
separated signals d = 1.01 (s, 3H, CH3), 1.15 (s, 3H, CH3), 3.27 (s,
3H, CH3); 13C NMR (75.5 MHz, CDCl3): major diastereomer
d = 23.6 (CH3), 27.8 (CH3), 30.6 (CH2), 33.5 (CH2), 36.1 (CH), 38.4
(CH2), 38.5 (C), 41.2 (CH2), 42.5 (CH), 43.3 (CH), 53.0 (CH), 56.9
(CH3), 84.6 (CH), 125.7 (CH), 126.6 (2ÂCH), 127.0 (CH), 128.1
(2ÂCH), 128.5 (2ÂCH), 129.3 (2ÂCH), 141.1 (C), 141.4 (C); minor
diastereomer—only separated signals d = 23.5 (CH3), 30.0 (CH2),
33.4 (CH2), 35.6 (CH), 41.1 (CH2), 43.1 (CH), 52.6 (CH), 56.8
(CH3); 77Se NMR (38.1 MHz, CDCl3): major diastereomer
d = 314.5 (Se); minor diastereomer d = 310.4 (Se) ppm. Elemental
analysis calcd for C25H32OSe (427.48): C, 70.24; H, 7.55; found: C,
70.01; H, 7.62.
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