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U. Grošelj et al.
PAPER
Table 4 NMR Data for (1R,5S)-4-Alkylidene-1,8,8-trimethyl-2-oxabicyclo[3.2.1]octan-3-ones 3–5 (continued)
Compound
1H NMR (d)
13C NMR (d)
3d
0.91 [3 H, t, J = 7.2 Hz, H3C(CH2)3], 0.94, 1.02, 1.32 (9 H, 3 s, 3 × 13.8, 18.1, 18.4, 22.3, 23.5, 27.2, 27.9, 30.7,
CH3), 1.28–1.53 (5 H, m, 2 × CH2, CHH), 1.97–2.23 (5 H, m, 2 ×
CH2, CHH), 2.77 (1 H, d, J = 6.0 Hz, HC5), 6.84 (1 H, t, J = 7.5 Hz,
HC4¢)
36.9, 44.1, 46.4, 92.1, 133.2, 142.0, 167.2
3e
0.93, 0.94 [6 H, 2d, J = 6.7 Hz, (CH3)2CH], 0.95, 1.01, 1.32 (9 H, 3 18.1, 18.4, 22.4, 22.6, 23.5, 27.7, 28.2, 36.6,
s, 3 × CH3), 1.44–1.53 (1 H, m, CHH), 1.70–1.85 [1 H, m,
CH(CH3)2], 1.97–2.21 (5 H, m, 2 × CH2, CHH), 2.78 (1 H, d, J = 6.0
Hz, HC5), 6.86 (1 H, t, J = 7.5 Hz, HC4¢)
36.8, 44.2, 46.4, 92.2, 133.7, 140.9, 167.1
3¢e
0.91, 0.93 [6 H, 2 d, J = 6.8 Hz, (CH3)2CH], 0.95, 0.98, 1.29 (9 H,
3 s, 3 × CH3), 1.50–1.63 (1 H, m, CHH), 1.65–1.76 [1 H, m,
CH(CH3)2], 1.92–2.20 (3 H, m, of CH2, CHH), 2.41 (1 H, d, J = 6.4
Hz, HC5), 2.47–5.57 (1 H, m, CHH), 2.63–2.73 (1 H, m, CHH),
5.88 (1 H, t, J = 7.2 Hz, H–C4¢)
3f
0.82–0.88 (3 H, m), 0.94–0.96 (3 H, m), 0.99–1.02 (6 H, m), 1.26– 11.90, 12.04, 18.00, 18.10, 18.31, 18.34, 19.81,
1.55 (3 H, m), 1.32 (3 H, s, CH3), 1.98–2.23 (3 H, m), 2.30–2.48 (1 20.03, 23.41, 23.44, 27.82, 28.17, 29.30, 29.56,
H, m), 2.79 (1 H, m), 6.62 (1 H, d, J = 10.6 Hz, H–C4¢)
33.87, 33.95, 36.84, 44.08, 44.10, 46.52, 46.62,
92.10, 92.20, 132.02, 132.14, 147.31, 147.32,
167.28, 167.33
3¢f
3g
0.81–0.89 (3 H, m), 0.94–0.99 (9 H, m), 1.15–1.45 (2 H, m), 1.29 (3 11.71, 11.92, 18.14, 18.21, 18.22, 18.41, 20.04,
H, s, CH3), 1.49–1.61 (1 H, m), 1.92–2.21 (3 H, m), 2.38 (1 H, d,
J = 6.0 Hz, HC5), 3.47–3.64 (1 H, m), 5.61 (1 H, t, J = 10.2 Hz,
HC4¢)
20.08, 23.43, 23.47, 28.24, 28.82, 30.02, 30.26,
33.65, 33.96, 37.03, 44.03, 44.08, 54.64, 54.73,
92.44, 92.59, 131.18, 131.22, 151.42, 151.77,
165.75, 165.82
0.95, 1.01, 1.31 (9 H, 3 s, 3 × CH3), 1.32–1.43 (2 H, m), 1.45–1.55 18.1, 18.4, 23.5, 25.4, 25.5, 28.2, 33.1, 33.3,
(1 H, m), 1.57–1.65 (2 H, m), 1.66–1.88 (4 H, m), 1.97–2.21 (3 H, 36.9, 38.3, 44.1, 46.7, 92.1, 131.8, 146.8, 167.4
m), 2.63–2.77 (1 H, m), 2.79 (1 H, d, J = 5.7 Hz, HC5), 6.76 (1 H,
d, J = 10.2 Hz, HC4¢)
3¢g
3h
3i
0.95, 0.98 (6 H, 2 s, 2 × CH3), 1.14–1.23 (2 H, m), 1.29 (3 H, s,
18.2, 18.3, 23.5, 25.5, 25.6, 28.5, 33.4, 33.7,
CH3), 1.49–1.70 (5 H, m), 1.84–2.19 (5 H, m), 2.37 (1 H, d, J = 6.0 37.0, 38.9, 44.1, 54.5, 92.5, 130.6, 150.9, 165.9
Hz, HC5), 3.74–3.88 (1 H, m), 5.77 (1 H, d, J = 9.4 Hz, HC4¢)
0.97, 1.04, 1.34 (9 H, 3 s, 3 × CH3), 1.51–1.60, 2.01–2.29 (4 H, 2 m, 18.4, 18.7, 23.7, 27.6, 37.0, 45.2, 49.5, 79.7,
2 × CH2), 3.15 (1 H, d, J = 6.0 Hz, HC5), 3.51 (1 H, d, J = 2.6 Hz, 89.7, 94.1, 117.3, 146.4, 166.1
HC∫C), 6.61 (1 H, d, J = 2.6 Hz, H–C4¢)
0.98, 1.04, 1.33 (9 H, 3 s, 3 × CH3), 1.48–1.56, 2.00–2.24 (4 H, 2 m, 18.1, 18.4, 23.4, 27.7, 33.6, 36.8, 44.3, 46.5,
2 × CH2), 2.92 (1 H, d, J = 5.7 Hz, HC5), 3.43–3.59 (2 H, m,
CH2Ph), 7.00 (1 H, dt, J = 0.8, 7.9, HC4¢), 7.15–7.32 (5 H, m, Ph)
92.3, 126.4, 128.4, 128.6, 133.8, 138.4, 139.2,
166.8
3j
0.99, 1.00, 1.35 (9 H, 3 s, 3 × CH3), 1.73–1.82, 2.06–2.37 (4 H, 2 m, 18.4, 18.9, 23.9, 28.4, 37.2, 45.0, 47.4, 93.5,
2 × CH2), 3.11 (1 H, d, J = 6.4 Hz, HC5), 7.32–7.44 (5 H, m, Ph),
7.76 (1 H, s, HC4¢)
129.0, 129.1, 130.0, 134.1, 135.4, 138.7, 168.2
3k
3l
0.96, 0.99, 1.35 (9 H, 3 s, 3 × CH3), 1.73–1.82, 2.04–2.35 (4 H, 2 m, 17.9, 18.4, 21.3, 23.4, 27.9, 36.8, 44.5, 46.9,
2 × CH2), 2.38 (3 H, s, CH3), 3.11 (1 H, d, J = 6.4 Hz, HC5), 7.19– 92.8, 129.2, 129.6, 132.1, 132.8, 138.2, 138.9,
7.27 (4 H, m, Ar), 7.73 (1 H, s, HC4¢)
167.8
0.96, 1.00, 1.35 (9 H, 3 s, 3 × CH3), 1.71–1.79, 2.04–2.37 (4 H, 2 m, 18.4, 18.9, 23.9, 28.2, 37.2, 45.0, 47.3, 93.1,
2 × CH2), 3.05 (1 H, d, J = 6.0 Hz, HC5), 7.06–7.13 (2 H, m, Ar),
7.30–7.36 (2 H, m, Ar), 7.70 (1 H, s, H–C4¢)
116.1 (JF–C(7¢) = 21.7 Hz), 131.5 (JF–C(5¢) = 3.2
Hz), 131.8 (JF–C(6¢) = 8.2 Hz), 134.0, 137.1, 163.1
(JF–C(8¢) = 249.9 Hz), 167.5
4
5
0.99, 1.08, 1.38 (9 H, 3 s, 3 × CH3), 1.55–1.64, 2.08–2.41 (4 H, 2 m, 18.4, 18.6, 23.6, 27.2, 36.7, 46.0, 50.9, 95.5,
2 × CH2), 3.19 (1 H, d, J = 6.8 Hz, HC5), 6.34 (1 H, s, HC4¢) 105.6, 115.5, 154.6, 163.5
0.95, 0.99, 1.34 (9 H, 3 s, 3 × CH3), 1.81–1.90, 2.01–2.12, and 2.21– 13.2, 18.5, 18.8, 24.0, 28.8, 37.3, 44.9, 48.4,
2.38 (4 H, 3 m, 2 × CH2), 2.41 (3 H, s, Me), 3.07 (1 H, d, J = 6.4 Hz, 93.6, 109.3, 111.3, 120.0, 120.6, 122.1, 127.4,
HC5), 7.09–7.18 (2 H, m, Ar), 7.31–7.34 (1 H, m, Ar), 7.49–7.52 (1 131.6, 132.8, 136.0, 137.1, 168.9
H, m, Ar), 7.81 (1 H, s, HC4¢), 8.70 (1 H, br s, NH)
Synthesis 2005, No. 7, 1087–1094 © Thieme Stuttgart · New York