M. Tiecco et al. / Tetrahedron: Asymmetry 15 (2004) 783–791
789
(s, 3H), 0.91 (s, 3H) 0.84 (s, 3H). 13C NMR: d 217.5,
206.6, 142.1, 129.2 (two carbons), 128.8 (two carbons),
126.3, 70.7, 58.4, 53.6, 49.4, 48.3, 47.2, 36.2, 32.1, 30.8,
29.3, 24.1, 20.0, 19.8, 10.0. 77Se NMR: d 492.8. Anal.
Calcd for C22H30O3Se: C, 62.70; H, 7.18. Found: C,
62.85; H, 7.28. Minor diastereoisomer (3R,4R) (distinct
1H, J ¼ 5:7 Hz), 2.14 (t, 1H, J ¼ 4:3 Hz), 1.95–1.55 (m,
3H), 1.50–1.28 (m, 1H), 1.0 (s, 3H), 0.90 (s, 3H) 0.80 (s,
3H). 13C NMR: d 218.0, 173.7, 159.7, 133.3, 128.0 (two
carbons), 114.2 (two carbons), 75.2, 58.6, 55.6, 52.8,
48.6, 47.6, 47.2, 45.2, 30.9, 23.8, 20.0, 19.9, 10.0. 77Se
NMR: d 535.6. Anal. Calcd for C21H28O5Se: C, 57.40;
H, 6.42. Found: C, 57.71; H, 6.55. Minor diastereoiso-
1
signals): H NMR: d 4.12–4.06 (m, 1H), 3.71 (dd, 1H,
1
J ¼ 2:1, 4.9 Hz), 3.66 (d, 1H, J ¼ 8:2 Hz), 2.99 (d, 1H,
J ¼ 7:2 Hz), 2.43 (s, 3H), 1.01 (s, 3H), 0.96 (s, 3H). 13C
NMR: d 217.7, 206.4, 142.4, 129.0 (two carbons), 126.2,
72.1, 58.6, 51.9, 48.8, 47.5, 47.3, 32.5, 30.1, 29.4, 23.9,
10.1. 77Se NMR: d 500.6.
mer (2R,3R) (distinct signals): H NMR: d 7.36 (A2B2
system, 2H), 5.04 (d, 1H, J ¼ 8:5 Hz), 3.98 (d, 1H,
J ¼ 8:5 Hz), 3.74 (s, 3H), 3.45 (dd, 1H, J ¼ 1:9, 4.6 Hz),
3.30 (br s, 1H), 1.98 (t, 1H, J ¼ 4:3 Hz), 0.95 (s, 3H),
0.87 (s, 3H), 0.75 (s, 3H). 13C NMR: d 173.2, 128.5, 75.5,
53.0, 45.8, 30.8, 23.6, 19.7. 77Se NMR: d 526.7.
4.22. (3S,4S) and (3S,4R)-5-(benzyloxy)-3-(camphor-
seleno)-4-hydroxypentan-2-one 6c and 7c
4.25. Methyl (2S,3S,4E)- and (2R,3R,4E)-2-(camphor-
seleno)-3-hydroxy-5-phenylpent-4-enoate 6f and 7f
Oil; 1H NMR: d 7.46–7.25 (m, 10H), 4.64–4.55 (m, 4H),
4.29–4.20 (m, 1H), 4.19–4.10 (m, 1H), 4.02 (dd, 1H,
J ¼ 4:0, 10.1 Hz), 3.94 (d, 1H, J ¼ 9:3 Hz), 3.91 (d, 1H,
J ¼ 8:6 Hz), 3.84 (dd, 1H, J ¼ 3:3, 10.1 Hz), 3.83–3.79
(m, 2H), 3.78–3.74 (m, 2H), 3.20 (br s, 1H), 2.99 (br s,
1H), 2.45 (s, 6H), 2.20–2.10 (m, 2H), 1.98–1.50 (m, 8H),
1.0 (s, 3H), 0.98 (s, 3H), 0.92 (s, 3H), 0.91 (s, 3H), 0.88
(s, 3H), 0.87 (s, 3H). 13C NMR: d 217.6 (two carbons),
205.2, 204.9, 137.9 (two carbons), 128.4 (four carbons),
127.8 (six carbons), 73.5 (two carbons), 71.6, 71.3, 71.2,
71.0, 58.2, 58.0, 49.0, 48.8, 48.5 (two carbons), 47.3,
47.0, 46.9, 46.8, 30.4 (two carbons), 28.7, 28.2, 23.6,
23.5, 19.6, 19.5, 19.4, 19.3, 9.6 (two carbons). 77Se
NMR: d 492.8 and 490.3. Anal. Calcd for C22H30O4Se:
C, 60.41; H, 6.91. Found: C, 60.75; H, 6.70.
1
Oil; Major diastereoisomer (2S,3S): H NMR: d 7.45–
7.20 (m, 5H), 6.77 (dd, 1H, J ¼ 1:1, 15.9 Hz), 6.37 (dd,
1H, J ¼ 6:0, 15.9 Hz), 4.80–4.70 (m, 1H), 4.15 (d, 1H,
J ¼ 5:3 Hz) 3.96 (dd, 1H, J ¼ 2:2, 4.7 Hz), 3.79 (s, 3H),
3.69 (d, 1H, J ¼ 8:9 Hz), 2.28 (t, 1H, J ¼ 4:6 Hz), 1.95–
1.55 (m, 3H), 1.52–1.40 (m, 1H), 1.03 (s, 3H), 0.96 (s,
3H), 0.93 (s, 3H). 13C NMR: d 218.4, 173.0, 136.4, 132.2,
128.5 (three carbons), 127.8, 126.7 (two carbons), 73.0,
58.2, 52.5, 48.5, 47.2, 46.9, 45.1, 30.5, 23.4, 19.6, 19.3,
9.6. 77Se NMR: d 521.7. Anal. Calcd for C22H28O4Se: C,
60.69; H, 6.48. Found: C, 60.79; H, 6.23. Minor dia-
stereoisomer (2R,3R) (distinct signals): 1H NMR: d 6.73
(dd, 1H, J ¼ 1:1, 15.9 Hz), 6.36 (dd, 1H, J ¼ 6:2,
15.9 Hz), 4.17 (dd, 1H, J ¼ 2:2, 4.6 Hz), 3.76 (d, 1H,
J ¼ 6:9 Hz), 3.43 (d, 1H, J ¼ 6:6 Hz), 2.47 (t, 1H,
J ¼ 4:4 Hz), 1.2 (s, 3H), 0.95 (s, 3H), 0.91 (s, 3H). 13C
NMR: d 217.4, 172.5, 136.3, 132.3, 128.2, 127.9, 73.2,
58.2, 48.4, 47.7, 43.9, 23.3, 19.4.
4.23. Methyl (2S,3S)- and (2R,3R)-2-(camphorseleno)-3-
hydroxy-3-phenylpropanoate 6d and 7d
1
4.26. Methyl (2S,3S)- and (2R,3R)-2-(camphorseleno)-3-
hydroxy-5-phenylpentanoate 6g and 7g
Oil; Major diastereoisomer (2S,3S): H NMR: d 7.48–
7.25 (m, 5H), 5.12 (dd, 1H, J ¼ 6:2, 7.9 Hz), 4.22 (d, 1H,
J ¼ 6:2 Hz), 3.80 (d, 1H, J ¼ 7:9 Hz), 3.70 (dd, 1H,
J ¼ 2:2, 4.7 Hz), 3.68 (s, 3H), 2.16 (t, 1H, J ¼ 4:3 Hz),
1.88–1.76 (m, 1H), 1.72–1.60 (m, 2H), 1.45–1.35 (m,
1H), 0.99 (s, 3H), 0.89 (s, 3H) 0.83 (s, 3H). 13 C NMR: d
217.6, 173.1, 140.7, 128.2 (two carbons), 127.8, 126.1
(two carbons), 75.0, 58.0, 52.3, 48.0, 46.9, 46.7, 44.3,
30.3, 23.2, 19.4, 19.3, 9.4. 77Se NMR: d 539.8. Anal.
Calcd for C20H26O4Se: C, 58.68; H, 6.40. Found: C,
58.77; H, 6.31. Minor diastereoisomer (2R,3R) (distinct
1
Oil; Major diastereoisomer (2S,3S): H NMR: d 7.35–
7.15 (m, 5H), 4.50 (br s, 1H), 3.93 (d, 1H, J ¼ 5:7 Hz),
3.91 (dt, 1H, J ¼ 3:5, 5.7 Hz), 3.85 (dd, 1H, J ¼ 2:1,
4.6 Hz), 3.76 (s, 3H), 2.95–2.88 (m, 1H), 2.80–2.69 (m,
1H), 2.11 (t, 1H, J ¼ 4:4 Hz), 2.15–2.01 (m, 1H), 1.94–
1.77 (m, 2H), 1.74–1.64 (m, 1H), 1.61–1.53 (m, 1H),
1.48–1.38 (m, 1H), 0.99 (s, 3H), 0.92 (s, 3H), 0.89 (s,
3H). 13C NMR: d 218.2, 173.4, 141.6, 128.5 (two car-
bons), 128.3 (two carbons), 125.8, 71.5, 58.1, 52.4, 48.6,
47.0, 46.8, 44.9, 36.6, 31.9, 30.4, 23.5, 19.6, 19.3, 9.5. 77Se
NMR: d 526.2. Anal. Calcd for C22H30O4Se: C, 60.41;
H, 6.91. Found: C, 60.60; H, 6.99. Minor diastereoiso-
mer (2R,3R) (distinct signals): 1H NMR: d 4.14 (dd, 1H,
J ¼ 2:3, 4.5 Hz), 4.0 (ddd, 1H, J ¼ 3:2, 6.3, 9.4 Hz), 3.52
(d, 1H, J ¼ 6:3 Hz), 2.20 (t, 1H, J ¼ 4:4 Hz), 1.1 (s, 3H),
0.93 (s, 3H), 0.81 (s, 3H). 13C NMR: d 217.0, 173.2, 71.9,
48.5, 47.3, 43.7, 32.0, 23.3, 19.4, 9.6.
1
signals): H NMR: d 5.07 (dd, 1H, J ¼ 1:2, 8.3 Hz), 4.0
(d, 1H, J ¼ 8:3 Hz), 3.72 (s, 3H), 3.50 (d, 1H,
J ¼ 1:2 Hz), 3.44 (dd, 1H, J ¼ 1:9, 4.6 Hz), 1.90 (t, 1H,
J ¼ 4:3 Hz), 0.92 (s, 3H), 0.86 (s, 3H) 0.73 (s, 3H). 13C
NMR: d 172.7, 128.1, 126.7, 75.3, 52.4, 46.8, 44.9, 30.1,
23.0, 19.1. 77Se NMR: d 527.9.
4.24. Methyl (2S,3S)- and (2R,3R)-2-(camphorseleno)-3-
hydroxy-3-(4-methoxyphenyl) propanoate 6e and 7e
4.27. Methyl (2S,3S)- and (2R,3R)-4-(benzyloxy)-2-
(camphorseleno)-3-hydroxybutanoate 6h and 7h
1
Oil; Major diastereoisomer (2S,3S): H NMR: d 7.30
(A2B2 system, 2H), 6.60 (A2B2 system, 2H), 5.06 (dd,
1H, J ¼ 5:7, 6.5 Hz), 4.16 (d, 1H, J ¼ 6:5 Hz), 3.79 (s,
3H), 3.73 (dd, 1H, J ¼ 2:2, 4.7 Hz), 3.71 (s, 3H), 3.63 (d,
1
Major diastereoisomer (2R,3R): H NMR d 7.40–7.25
(m, 5H), 4.59 (d, 1H, J ¼ 11:8 Hz), 4.56 (d, 1H, J ¼ 11:8