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(s, 3H), 3.53 (ddd, 1H, J=4.2, 9.4, 10.4 Hz), 3.40 (ddd,
1H, J=4.2, 9.4, 11.2 Hz), 2.93 (dd, 1H, J=10.4, 14.9
Hz),), 2.08 (dd, 1H, J=4.6, 14.9 Hz), 2.02–1.9 (m, 1H),
1.80–1.74 (m, 2H), 1.52–1.25 (m, 5H). 13C NMR: l
172.2, 138.5, 128.8 (two carbons), 127.9, 125.9 (two
carbons), 81.9, 79.7, 74.5, 72.4, 52.0, 32.2, 30.6, 30.5,
24.7 (two carbons). MS m/z (rel. int.): 290 (1), 216 (35),
193 (69), 192 (39), 161 (41), 160 (28), 133 (8), 117 (10),
115 (15), 107 (100), 105 (11), 103 (12), 91 (18), 82 (28),
67 (45), 54 (12). Anal. calcd for C17H22O4: C, 70.32; H,
7.64. Found: C, 70.30, H, 7.71%.
J=8.9 Hz), 4.07 (ddd, 1H, J=3.8, 8.7, 8.9 Hz), 3.49 (s,
3H), 3.45–3.32 (m, 2H), 2.39 (dd, 1H, J=8.7, 15.5 Hz),
2.21 (dd, 1H, J=3.8, 15.5 Hz), 2.0–1.82 (m, 1H),
1.80–1.70 (m, 2H), 1.52–1.25 (m, 5H). 13C NMR: l
171.5, 138.2, 129.0 (three carbons), 128.2 (two carbons),
83.3, 80.5, 80.3, 77.8, 52.0, 37.3, 30.6, 30.5, 24.6, 24.5.
MS m/z (rel. int.): 290 (1), 216 (27), 193 (56), 192 (27),
161 (33), 160 (23), 133 (9), 117 (13), 115 (17), 107 (100),
105 (12), 103 (13), 91 (18), 82 (29), 67 (51), 54 (16).
Anal. calcd for C17H22O4: C, 70.32; H, 7.64. Found: C,
70.30, H, 7.71%.
4.4.4. Methyl [(2R,3S,5R,6R)-5,6-dimethyl-3-phenyl-1,4-
dioxan-2-yl]acetate, 5d. Oil; [h]2D7=+25.3 (c 0.26,
4.4.8. Methyl [(2S,3S,5R,6R)-5,6-dimethyl-3-phenyl-1,4-
dioxan-2-yl]acetate, 6d. Oil; [h]3D0=+26.3 (c 0.34,
1
1
CHCl3). H NMR: l 7.40–7.20 (m, 5H), 4.95 (d, 1H,
CHCl3). H NMR: l 7.35–7.20 (m, 5H), 4.29 (d, 1H,
J=3.4 Hz), 4.42 (ddd, 1H, J=3.4, 4.4, 10.4 Hz), 3.64
(dq, 1H, J=6.1, 9.2 Hz), 3.57 (s, 3H), 3.50 (dq, 1H,
J=6.2, 9.2 Hz), 2.88 (dd, 1H, J=10.4, 14.8 Hz), 2.05
(dd, 1H, J=4.4, 14.8 Hz), 1.25 (d, 3H, J=6.2 Hz), 1.11
(d, 3H, J=6.1 Hz). 13C NMR: l 172.3, 138.5, 128.8
(two carbons), 127.9, 125.8 (two carbons), 79.1, 78.8,
74.1, 69.5, 52.0, 32.0, 17.9, 17.8. MS m/z (rel. int.): 264
(1), 233 (4), 220 (5), 193 (62), 176 (13), 161 (62), 160
(28), 133 (15), 117 (39), 115 (28), 107 (100), 105 (21),
103 (13), 91 (31), 79 (20), 77 (15), 56 (45). Anal. calcd
for C15H20O4: C, 68.16; H, 7.63. Found: C, 68.10; H,
7.61%.
J=9.1 Hz), 3.99 (ddd, 1H, J=3.8, 8.7, 9.1 Hz), 3.57 (s,
3H), 3.51 (dq, 1H, J=6.1, 8.7 Hz), 3.46 (dq, 1H,
J=6.0, 8.7 Hz), 2.37 (dd, 1H, J=8.7, 15.4 Hz), 2.20
(dd, 1H, J=3.8, 15.4 Hz), 1.19 (d, 3H, J=6.0 Hz), 1.17
(d, 3H, J=6.1 Hz). 13C NMR: l 171.6, 138.3, 129.0
(two carbons), 128.8, 128.2 (two carbons), 82.9, 77.8,
77.7, 77.6, 52.0, 37.3, 17.8, 17.7. MS m/z (rel. int.): 264
(1), 233 (12), 220 (5), 193 (63), 176 (12), 161 (54), 160
(28), 133 (18), 117 (41), 115 (28), 107 (100), 105 (22),
103 (13), 91 (26), 79 (19), 77 (15), 56 (46). Anal. calcd
for C15H20O4: C, 68.16; H, 7.63. Found: C, 68.07; H,
7.69%.
4.4.5. [(2S,3S,5R,6R)-3-Methyl-5,6-diphenyl-1,4-dioxan-
2-yl]acetonitrile, 6a. Oil; [h]2D1=+96.0 (c 1.67, CHCl3).
1H NMR: l 7.20–7.15 (m, 6H), 6.90–6.80 (m, 4H) 4.45
(d, 1H, J=9.1 Hz), 4.42 (d, 1H, J=9.1 Hz), 3.87 (dq,
1H, J=6.3, 9.1 Hz), 3.69 (dt, 1H, J=4.6, 9.1 Hz), 2.70
(dd, 1H, J=4.6, 17.1 Hz), 2.57 (dd, 1H, J=4.6, 17.1
Hz), 1.28 (d, 3H, J=6.3 Hz). 13C NMR: l 137.5, 137.3,
128.6 (two carbons), 128.4 (two carbons), 128.3 (two
carbons), 128.0 (two carbons), 127.9 (two carbons),
117.7, 84.7, 84.6, 76.0, 75.0, 21.0, 17.6. MS m/z (rel.
int.): 293 (43), 187 (11), 180 (10), 179 (10), 178 (14), 165
(9), 152 (5), 107 (100), 106 (34), 105 (73), 82 (30), 79
(22), 77 (29), 55 (5), 51 (5). Anal. calcd for C19H19NO2:
C, 77.79; H, 6.53, N, 4.77. Found: C, 77.83, H, 6.50, N,
4.71%.
4.4.9. (2S,3R,5R,6R)- and (2R,3R,5R,6R)-[3-Methyl-
5,6-diphenyl-1,4-dioxan-2-yl]acetonitriles, 9a and 10a.
1
Oil; (mixture of isomers 9a:10a=12:88); 10a H NMR:
l 7.30–7.15 (m, 6H), 7.15–7.00 (m, 4H) 4.69 (d, 1H,
J=9.4 Hz), 4.51 (d, 1H, J=9.4 Hz), 4.45 (dt, 1H,
J=3.1, 7.2 Hz), 4.28 (dq, 1H, J=3.1, 6.7 Hz), 2.65 (dd,
1H, J=7.2, 16.8 Hz), 2.52 (dd, 1H, J=7.2, 16.8 Hz)
1.57 (d, 3H, J=6.7 Hz). 13C NMR: l 137.6, 137.4,
128.7, 128.6, 128.5 (two carbons), 128.4 (two carbons),
128.0 (two carbons), 127.9 (two carbons), 116.9, 85.7,
76.1, 73.7, 70.2, 20.9, 11.9. MS m/z (rel. int.): 293 (43),
187 (11), 180 (10), 179 (10), 178 (14), 165 (9), 152 (5),
107 (100), 106 (34), 105 (73), 82 (30), 79 (22), 77 (29), 55
(5), 51 (5). Anal. calcd for C19H19NO2: C, 77.79; H,
6.53, N, 4.77. Found: C, 77.83, H, 6.50, N, 4.71%.
1
4.4.6. Methyl [(2S,3S,5R,6R)-3,5,6-triphenyl-1,4-dioxan-
9a (distinct signals): H NMR: l 4.91 (d, 1H, J=8.1
1
2-yl]acetate, 6b. Oil; [h]2D1=+31.1 (c 0.79, CHCl3). H
Hz), 4.75 (d, 1H, J=8.1 Hz), 4.09 (dq, 1H, J=2.3, 6.6
Hz), 4.06 (dt, 1H, J=2.3, 6.8 Hz), 3.08 (dd, 1H, J=6.8,
16.7 Hz), 3.13 (dd, 1H, J=6.8, 16.7 Hz), 1.61 (d, 3H,
J=6.6 Hz). 13C NMR: l 138.0, 137.7, 128.8, 128.2,
128.1, 76.9, 75.7, 71.6, 69.2, 20.5, 17.3.
NMR: l 7.50–7.45 (m, 2H), 7.35–7.25 (m, 2H), 7.20–
7.08 (m, 7H), 7.03–6.98 (m, 4H), 4.65 (d, 1H, J=9.2
Hz), 4.64 (d, 1H, J=9.0 Hz), 4.53 (d, 1H, J=9.0 Hz),
4.28 (ddd, 1H, J=4.1, 7.8, 9.2 Hz), 3.50 (s, 3H), 2.48
(dd, 1H, J=7.8, 15.6 Hz), 2.35 (dd, 1H, J=4.1, 15.6
Hz). 13C NMR: l 171.4, 138.0, 137.9, 137.8, 129.1 129.0
(two carbons), 128.4, 128.3 (three carbons), 128.2 (two
carbons), 128.1(two carbons), 128.0 (two carbons),
127.9 (two carbons), 84.7, 84.6, 82.7, 77.8, 52.1, 37.2.
MS m/z (rel. int.): 388 (1), 282 (4), 281 (3), 207 (6), 192
(3), 176 (100), 165 (5), 144 (3), 134 (10), 117 (59), 115
(14), 105 (7), 91 (9), 77 (6). Anal. calcd for C25H24O4: C,
77.30; H, 6.23. Found: C, 77.23, H, 6.18%.
4.4.10. Methyl [(2R,3R,5R,6R)-5,6-dimethyl-3-phenyl-
1,4-dioxan-2-yl]acetate, 9d. Oil; [h]2D7=+18.4 (c 0.95,
CHCl3). H NMR: l 7.55–7.25 (m, 5H), 4.62 (d, 1H,
1
J=5.2 Hz), 4.55 (dt, 1H, J=5.2, 8.1 Hz), 3.75 (dq, 1H,
J=5.4, 6.4 Hz), 3.70 (s, 3H), 3.60 (dq, 1H, J=5.4, 6.4
Hz), 2.78 (dd, 1H, J=8.1, 15.1 Hz), 2.60 (dd, 1H,
J=5.2, 15.1 Hz), 1.32 (d, 3H, J=6.4 Hz), 1.28 (d, 3H,
J=6.4 Hz). 13C NMR: l 171.8, 139.0, 128.9 (two
carbons), 128.6, 128.5, (two carbons), 74.9, 71.3, 71.0,
69.9, 52.2, 37.1, 17.7, 17.6. MS m/z (rel. int.): 264 (1),
233 (3), 220 (4), 193 (47), 176 (13), 161 (58), 160 (25),
133 (18), 117 (74), 115 (35), 107 (100), 105 (25), 103
4.4.7. Methyl [(2S,3S,4aR,8aR)-3-phenyloctahydro-1,4-
benzodioxin-2-yl]acetate, 6c. Oil; [h]2D3=+22.1 (c 0.30,
1
CHCl3). H NMR: l 7.40–7.25 (m, 5H), 4.36 (d, 1H,