18
ACCEPTED MANUSCRIPT
313.1426, calcd for C17H22O4Na [M + Na+] 313.1416. Anal. Calcd for C17H22O4: C,
70.32; H, 7.64. Found: C, 70.34; H, 7.81.
anti-2b: Colorless granules; mp 134.5−136.5 °C (dec.) (from hexane−CH2Cl2). 1H
NMR (500 MHz, CDCl3): δH 0.78 (s, 3H), 1.00 (t, J = 7.3 Hz, 3H), 1.13−1.17 (m, 1H),
1.28 (s, 3H), 1.35−1.55 (m, 5H), 1.62−1.65 (m, 1H), 1.85−1.92 (m, 1H), 4.33 (d, J = 7.8
Hz, 1H), 4.50 (dd, J = 7.8 and 1.8 Hz, 1H), 5.36 (s, 1H), 6.84 (dd, J = 7.8 and 2.7 Hz,
1H), 7.09 (s with fine coupling, 1H), 7.16 (d, J = 7.8 Hz, 1H), 7.25 (t, J = 7.8 Hz, 1H)
ppm. 13C NMR (125 MHz, CDCl3): δC 9.42, 17.7, 22.3, 22.6, 22.8, 27.9, 35.6, 36.1,
48.8, 74.1, 106.3, 113.7, 114.6, 116.5, 120.0, 129.5, 136.1, 155.5 ppm. IR (KBr): ν
3449, 2967, 2940, 1604, 1218 cm-1. Mass (m/z, %): 304 (M+, 7), 217 (14), 166 (60), 138
̃
(81), 121 (100), 109 (23). HRMS (ESI): 327.1560, calcd for C18H24O4Na [M + Na+]
327.1572. Anal. Calcd for C18H24O4: C, 71.03; H, 7.95. Found: C, 71.01; H, 8.15.
anti-2c: Colorless plates; mp 142.5−145.0 °C (dec.) (from hexane−CH2Cl2). 1H NMR
(500 MHz, CDCl3): δH 0.88 (s, 3H), 1.22−1.27 (m, 1H), 1.34 (s, 3H), 1.36−1.58 (m, 3H),
1.72−1.77 (m, 1H), 1.82−1.92 (m, 1H), 2.69 (d, J = 13.3 Hz, 1H), 3.17 (d, J = 13.3 Hz,
1H), 4.22 (d, J = 8.2 Hz, 1H), 4.34 (d with fine coupling, J = 8.2 Hz, 1H), 5.20 (s, 1H),
6.86−6.91 (m, 1H), 7.22−7.38 (m, 8H) ppm. 13C NMR (125MHz, CDCl3): δC 17.8, 22.5,
23.2, 27.9, 35.5, 35.6, 36.3, 49.2, 73.7, 106.0, 113.7, 114.7, 116.7, 120.1, 126.7, 128.4
(x 2), 129.7, 130.9 (x 2), 136.1, 137.9, 155.5 ppm. IR (KBr): ν̃ 3428, 2939, 1604, 1220
cm-1. Mass (m/z, %): 229 (M+-137, 21), 228 (100), 213 (17). HRMS (ESI): 389.1728,
calcd for C23H26O4Na [M + Na+] 389.1729. Anal. Calcd for C23H26O4: C, 75.38; H, 7.15.
Found: C, 75.18; H, 7.29.
1
anti-2d: Pale yellow amorphous solid. H NMR (600 MHz, CDCl3): δH 0.73 (s, 3H),
1.11−1.14 (m, 1H), 1.24 (s, 3H), 1.34−1.48 (m, 3H), 1.37 (s, 3H), 1.54−1.65 (m, 2H),
3.95 (d, J = 7.5 Hz, 1H), 4.68 (d with fine coupling, J = 7.5 Hz, 1H), 5.19 (s, 1H), 6.84
(d with fine coupling, J = 8.8 Hz, 2H), 7.50 (d with fine coupling, J = 8.7 Hz, 2H) ppm.
13C NMR (150 MHz, CDCl3): δC 18.0, 22.0, 22.5, 27.1, 27.2, 35.5, 36.1, 44.6, 80.8,
105.1, 114.3, 115.1 (CH x 2), 126.9, 129.2 (CH x 2), 156.6 ppm. IR (KBr): ν̃ 3365,
2935, 1613, 1517, 1445, 1325, 1277, 1227, 1016, 983 cm-1. Mass (m/z, %): 290 (M+, 2),
258 (10), 243 (15), 152 (26), 138 (15), 124 (15), 123 (10), 121 (100), 82 (10), 69 (11).
HRMS (ESI): 313.1402, calcd for C17H22O4Na [M + Na+] 313.1416.
1
anti-2e: Colorless columns; mp 110.0-112.0 °C (from hexane−CH2Cl2). H NMR (600
MHz, CDCl3): δH 0.75 (s, 3H), 1.10−1.15 (m, 1H), 1.26 (s, 3H), 1.36−1.50 (m, 3H),
1.39 (s, 3H), 1.56−1.65 (m, 2H), 3.83 (s, 3H), 3.98 (d, J = 7.5 Hz, 1H), 4.71 (d, J = 7.5
Hz, 1H), 6.93 (dd, J = 8.2 and 2.6 Hz, 1H), 7.18 (s with fine coupling, 1H), 7.21 (broad
d with fine coupling, J = 7.7 Hz, 1H), 7.32 (dd, J = 8.2 and 7.7 Hz, 1H) ppm. 13C NMR