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21. Alternatively we have prepared the α,β-unsaturated ketone 7 directly from natural shikimic acid by sequential
esterification, transacetalisation and oxidation. The key step was the transacetalisation in which methyl shikimate was
treated with 2,2,3,3-tetramethoxybutane to form a separable mixture of the desired butane 2,3-diacetal (formed with the
pseudo-trans-diequatorial 4,5-dihydroxyl groups in the shikimate) together with butane 2,2-diacetal (formed with the 3,4-
dihydroxyl groups) in a ratio of 2:1.
22. All new compounds reported had spectral data in accord with the assigned structure and gave satisfactory elemental
analyses and/or high resolution mass spectral data. Selected data: compound 2: νmax (KBr)/cm−1 3394, 2927, 1712 (C_O),
1662 (C_C), 1430, 1295, 1164, 1114, 1014; δH (270 MHz, CD3OD) 2.26 (1H, dm, J 18.47 Hz, CHHC_), 2.90 (1H, ddt, J
0.67, 18.47 and 4.61 Hz, CHHC_), 3.68–3.90 (2H, m, 2×CHOH), 6.63 (1H, apparent dt, J 7.91 and 2.64 Hz, CH_C); δC
(67.8 MHz, CD3OD) 33.41 (CH2), 68.87 (d, JFC 7.27 Hz, CH2CHOH), 75.14 (dd, JFC 19.73 and 20.77 Hz, CF2CHOH),
121.30 (t, JFC 237.80 Hz, CF2), 130.00 (dd, JFC 27.0 and 32.19 Hz, CH_C), 137.54 (dd, JFC 10.38 and 11.43 Hz, CH_C),
168.14 (C_O); δF (254 MHz, CDCl3) −103.4 (dm, JFF 284.1 Hz), −105.4 (dm, JFF 284.1 Hz) (found: C, 43.25; H, 4.07.
C7H8F2O4 requires: C, 43.31; H, 4.15%). Compound 3: νmax (KBr)/cm−1 3347, 2958, 2927, 1704 (C_O), 1654 (C_C),
1257, 1153, 1060, 1044; δH (270 MHz, CD3OD) 2.38–2.54 (1H, m, CHHC_), 2.67 (1H, dm, J 18.47 Hz, CHHC_),
3.95–4.01 (2H, m, 2×CHOH), 6.61 (1H, dm, J 7.26 Hz, CH_C); δC (67.8 MHz, CD3OD) 29.94 (CH2), 68.03 (d, JFC 6.23
Hz, CH2CHOH), 72.25 (dd, JFC 18.69 and 31.15 Hz, CF2CHOH), 119.88 (dd, JFC 233.13 and 242.50 Hz, CF2), 129.01
(dd, JFC 25.96 and 34.27 Hz, CH_C), 138.93 (t, JFC 10.39 Hz, CH_C), 168.31 (C_O) [m/z HRMS (CI, NH3). Found
MNH4+, 212.0727; C7H12F2NO4 requires MNH4, 212.0734]. Compound 8: νmax (film)/cm−1 2996, 2954, 2911, 2838, 1731
(C_O), 1658 (C_C), 1438, 1373, 1303, 1265, 1230, 1118, 1037; δH (270 MHz, CDCl3) 1.32 (3H, s, Me), 1.40 (3H, s,
Me), 2.27–2.46 (1H, m, CHHC_), 2.90 (1H, dt, J 18.47 and 5.28 Hz, CHHC_), 3.28 (3H, s, OMe), 3.32 (3H, s, OMe),
3.81 (3H, s, CO2Me), 3.87–4.09 (2H, m, 2×CHOR), 6.72 (1H, dt, J 8.57 and 2.64 Hz, CH_C); δC (67.8 MHz, CDCl3)
17.48 (Me), 17.61 (Me), 29.60 (CH2), 48.07 (OMe), 48.10 (OMe), 52.56 (CO2Me), 64.08 (d, JFC 8.3 Hz, CH2CHOR),
70.86 (dd, JFC 18.69 and 20.77 Hz, CF2CHOR), 99.27 (CHOR), 99.94 (CHOR), 116.86 (dd, JFC 239.35 and 242.47 Hz,
CF2), 130.02 (dd, JFC 24.93 and 33.23 Hz, CH_C), 134.94 (t, JFC 10.39 Hz, CH_C), 165.30 (C_O) [m/z HRMS (CI,
NH3). Found MNH4+, 340.1572; C14H24F2NO6 requires MNH4, 340.1572].
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