3400
S. Bhosale et al. / Tetrahedron Letters 52 (2011) 3397–3400
J = 4.2 Hz, 1H), 5.12 (s, 2H), 5.83 (d, J = 3.7 Hz, 1H), 6.66 (dd, J = 8.3, 1.0 Hz, 1H),
H
6.76 (d, J = 1.0 Hz, 1H), 6.79 (d, J = 8.1 Hz, 1H), 7.27–7.30 (aromatics, 1H), 7.35
(t, J = 7.6 Hz, 2H), 7.43 (d, J = 7.6 Hz, 2H). 13C NMR (100 MHz; CDCl3): d 26.44,
26.92, 32.30, 36.43, 39.26, 56.24, 71.57, 77.36, 80.86, 105.55, 111.06, 112.76,
114.74, 120.50, 127.55(2C), 127.99, 128.74 (2C), 135.39, 137.74, 146.71,
149.93. HPLC-MS (m/z): 402.3 [M+18] base peak, HPLC purity: 97%, rt:
15.66 min.
O
D-Glucose
OHC
diacetonide
O
5 steps
O
14. 7: Rf-value: 0.3 (60% ethyl acetate in hexanes). Mp: 74–76 °C. ½a D25
ꢀ
+11.66 (c 1.0,
OH OH
CHCl3). 1H NMR (400 MHz; CDCl3): d 1.70–1.90 (m, 3H, –CH2–, –OH), 1.90–2.10
(m, 2H), 2.54–2.74 (m, 2H+0.66H, –CH2– and –OH), 3.02 (s, 0.33H, –OH), 3.87
(s, 3H), 4.24–4.36 (m, 2H), 5.12 (s, 2H), 5.26 (s, 0.33H, anomeric-H), 5.38 (d,
J = 3.4 Hz, 0.66H, anomeric-H), 6.65 (d, J = 8.0 Hz, 1H), 6.74 (s, 1H), 6.79 (d,
J = 8.0 Hz, 1H), 7.27–7.31 (aromatics, 1H), 7.36 (t, J = 7.4 Hz, 2H), 7.43 (d,
J = 7.3 Hz, 2H). 13C NMR (100 MHz; CDCl3): d [31.92, 32.21, 37.71, 38.06, 38.53,
39.52 account for 3C)], 56.21, 71.40, 71.82 (0.7C), 76.48 (0.7C), 76.80 (0.3C),
79.42 (0.3C), 96.97 (0.7C), 102.81 (0.3C), 112.60, 114.46, 120.45, 127.55 (2C),
128.00, 128.71 (2C), 135.18, 137.50, 146.55, 149.71. HPLC-MS (m/z): 362.2
[M+18] base peak, HPLC purity: 94.0%, rt: 11.68 min.
7-8 steps
OR
R = Me, H
.
9. (a) Kucera, D.; Haley, G. J.; Rueden, E. J.; Wang, T. in PCT Publication No.
WO2008/140549 A1.; (b) Suresh, V.; Selvam, J. J. P.; Rajesh, K.; Venkateswarlu,
Y. Tetrahedron: Asymmetry 2008, 19, 1509–1513.
10. (Z)-9: Rf-value: 0.6 (30% ethyl acetate in hexanes). Mp: 117–119 °C. ½a D25
ꢀ
+67.9
(c 1.0, CHCl3). 1H NMR (400 MHz; CDCl3): d 1.32 (s, 3H), 1.44 (s, 3H), 1.71 (ddd,
J = 15.6, 11, 4.6 Hz, 1H), 2.21 (dd, J = 13.4, 4.1 Hz, 1H); 3.93 (s, 3H), 4.78 (t,
J = 4.1 Hz, 1H), 5.06 (dt, J = 10.7, 3.9 Hz, 1H), 5.17 (s, 2H), 5.55 (dd, J = 11.2,
8.8 Hz, 1H), 5.89 (d, J = 3.9 Hz, 1H), 6.63 (d, J = 11.5 Hz, 1H), 6.79 (dd, J = 8.3,
1.7 Hz, 1H), 6.84 (d, J = 8.3 Hz, 1H), 7.07 (d, J = 1.2 Hz, 1H), 7.27–7.31
(aromatics, 1H), 7.36 (t, J = 7.6 Hz, 2H), 7.43 (d, J = 7.4 Hz, 2H). 13C NMR
(100 MHz; CDCl3): d 26.36, 26.89, 40.41, 56.16, 71.13, 73.96, 80.97, 105.55,
111.03, 112.53, 113.70, 121.84, 127.47(2C), 127.63, 128.07, 128.79 (2C),
129.89, 134.74, 137.25, 147.87, 149.51. HPLC-MS (m/z): 400.3 [M+18] base
peak, HPLC purity: 99.0%, rt: 15.6 min.
15. Motoshima, K.; Noguchi-Yachide, T.; Sugita, K.; Hashimoto, Y.; Ishikawa, M.
Bioorg. Med. Chem. 2009, 17, 5001–5014.
16. (Z)-8. Rf-value: 0.6 (60% ethyl acetate in hexanes). Mp: 64–65 °C. ½a D25
ꢀ
+20.36 (c
0.5 in CHCl3). 1H NMR (400 MHz; CDCl3): d 1.67–1.82 (m, 4H), 2.56–2.72 (m,
2H), 2.76 (br s, 1H, –OH), 2.99 (br s, 1H, –OH), 3.85–3.94 (m, 1H), 3.86 (s, 6H, –
OMe), 4.85 (t, J = 8.3 Hz, 1H), 5.12 (s, 2H), 5.16 (s, 2H), 5.59 (dd, J = 11.2, 9.3 Hz,
1H), 6.45 (d, J = 11.7 Hz, 1H), 6.65 (d, J = 7.8 Hz, 1H), 6.74 (s, 1H), 6.76–6.82
(aromatics, 2H), 6.84 (d, J = 8.3 Hz, 1H), 6.88 (s, 1H), 7.30 (app. t, J = 6.8 Hz, 2H),
7.30–7.40 (aromatics, 4H), 7.43 (d, J = 7.4 Hz, 4H). 13C NMR (100 MHz; CDCl3):
d 31.65, 40.17, 43.76, 56.33(2C), 69.38, 71.34, 71.59, 72.01, 112.71, 113.05,
114.06, 114.70, 120.53, 121.70, 127.58 (2C), 127.62 (2C), 128.09, 128.22,
128.83 (2C), 128.91 (2C), 130.14, 131.18, 132.84, 135.47, 137.36, 137.73,
146.78, 148.02, 149.72, 150.01. HPLC-MS (m/z): 572.4 [M+18] base peak, HPLC
11. (E)-9. Rf-value: 0.65 (30% ethyl acetate in hexanes). Mp: 121–123 °C. ½a D25
ꢀ ꢁ15.5
(c 0.2, CHCl3). 1H NMR (400 MHz; CDCl3): d 1.35 (s, 3H), 1.56 (s, 3H), 1.71 (ddd,
J = 13.7, 10.8, 4.9 Hz, 1H), 2.23 (dd, J = 13.7, 4.4 Hz, 1H); 3.89 (s, 3H), 4.76–4.82
(m, 2H), 5.16 (s, 2H), 5.89 (d, J = 3.9 Hz, 1H), 6.02 (dd, J = 15.7, 7.3 Hz, 1H), 6.60
(d, J = 16 Hz, 1H), 6.81 (d, J = 8.3 Hz, 1H), 6.84 (dd, J = 8.3, 2 Hz, 1H), 6.96 (d,
J = 2 Hz, 1H), 7.28–7.31 (aromatics, 1H), 7.36 (t, J = 7.3 Hz, 2H), 7.43 (d,
J = 7.3 Hz, 2H). 13C NMR (100 MHz; CDCl3): d 26.18, 26.76, 39.87, 55.98, 70.99,
78.70, 80.67, 105.43, 109.37, 111.09, 113.76, 119.90, 125.54, 127.29 (2C),
127.93, 128.63(2C), 129.96, 132.54, 137.06, 148.22, 149.68. HPLC-MS (m/z):
383.2 [M+1], 400.2 [M+18] base peak, purity: 99.44%, rt: 17 min.
purity: 99%, rt: 16.12 min. IR (neat): 3401, 2936, 1602, 1514 cmꢁ1
.
17. (Z)-12. Rf-value: 0.6 (40% ethyl acetate in hexanes). Mp: 66–69 °C. ½a D25
ꢀ
+34.0 (c
1.0, CHCl3). 1H NMR (400 MHz; CDCl3): d 1.66–1.84 (m, 4H and –OH), 2.58–
2.73 (m, 2H and -OH), 3.86 (s, 3H), 3.88–3.95 (m, 1H), 4.84 (dt, J = 9.3, 2.9 Hz,
1H), 5.12 (s, 2H), 5.68 (dd, J = 11.7, 9.3 Hz, 1H), 6.54 (d, J = 11.7 Hz, 1H), 6.65
(dd, J = 8.3, 2.0 Hz, 1H), 6.74 (d, J = 2.0 Hz, 1H), 6.79 (d, J = 7.8 Hz, 1H), 7.27–
7.34 (aromatics, 6H), 7.36 (app. t, J = 7.3 Hz, 2H), 7.43 (d, J = 7.4 Hz, 2H). 13C
NMR (100 MHz; CDCl3): d 31.38, 39.83, 43.17, 56.03, 69.03, 71.24, 71.71,
112.32, 114.27, 120.26, 127.35 (2C), 127.47, 127.84, 128.48 (2C), 128.60 (2C),
128.83 (2C), 130.84, 133.88, 135.22, 136.49, 137.45, 146.40, 149.63. HPLC-MS
(m/z): 436.2 [M+18] base peak, HPLC purity: 98.52%, rt: 16.27 min.
12. Jourdant, A.; González-Zamora, E.; Zhu, J. J. Org. Chem. 2002, 67, 3163–3164.
13. 10: Rf-value: 0.6 (30% ethyl acetate in hexanes). Mp: 61–63 °C. ½a D25
ꢀ ꢁ5.6 (c 1.0,
CHCl3). 1H NMR (400 MHz; CDCl3): d 1.32 (s, 3H), 1.43–1.51 (m, 1H), 1.48 (s,
3H), 1.79–1.84 (m, 1H), 1.85–1.95 (m, 1H), 2.08 (dd, J = 13.2, 4.1 Hz, 1H), 2.57–
2.65 (m, 1H), 2.68–2.76 (m, 1H), 3.88 (s, 3H), 4.16–4.24 (m, 1H), 4.72 (t,