460
H. M. Sirat et al. / Tetrahedron Letters 48 (2007) 457–460
(300 MHz, CDCl3) d 1.11 (3H, s, H-12), 1.14 (3H, s, H-13),
References and notes
1.22 (3H, d, J 6.9 Hz, H-15), 1.34 (2H, m, H-9 and H-90),
1.58 (1H, m, H-80), 1.85 (1H, m, H-8), 2.21 (3H, s, H-14),
2.61 (1H, sext, J 6.9 Hz, H-7), 3.30 (1H, dd, J 9.9, 2.1 Hz, H-
10), 6.62 (1H, d, J 1.8 Hz, H-2), 6.67 (1H, dd, J 7.8, 1.8 Hz,
H-6), 7.02 (1H, d, J 7.8 Hz, H-5); 13C NMR (75 MHz,
CDCl3) d 15.3 (C-14), 23.1 (C-15), 23.4 (C-12), 26.5 (C-13),
29.9 (C-9), 35.5 (C-8), 39.7 (C-7), 73.1 (C-11), 78.8 (C-10),
113.4 (C-2), 119.1 (C-6), 121.1 (C-4), 130.9 (C-5), 146.9 (C-
1), 153.8 (C-3); EIMS m/z 252 (11) [M+, C15H24O3], 234 (2)
[MꢀH2O]+, 216 (3), 194 (17), 175 (36), 161 (15), 148 (47),
135 (100), 121 (31), 109 (17), 91 (52), 77 (28).
1. (a) Rimpler, H.; Ha¨nsel, R.; Kochendoerfer, L. Z.
Naturforsch. 1970, 25, 995–998; (b) John, T. K.; Rao, K.
Indian. J. Chem. 1985, 24B, 35–37.
2. Hwang, J.-K.; Shim, J.-S.; Baek, N.-I.; Pyun, Y.-R. Planta
Med. 2000, 66, 196–197.
3. (a) Mane, R. B.; Rao, G. S. K. Indian J. Chem. 1974, 12B,
938–939; (b) ApSimon, J. In The Total Synthesis of
Natural Products; John Wiley & Sons: USA, 1983; Vol. 5,
pp 42–43; (c) Garcia, G. E.; Mendoza, V.; Guzman, B. A.
J. Nat. Prod. 1987, 50, 1055–1058; (d) Krause, W.;
Bohlmann, F. Tetrahedron Lett. 1987, 28, 2575–2578; (e)
Rane, R. K.; Desai, U. V.; Mane, R. B. Indian J. Chem.
1987, 26B, 572–573; (f) Nagumo, S.; Irie, S.; Hayashi, K.;
Akita, H. Heterocycles 1996, 43, 1175–1178; (g) Meyers,
A. I.; Stoianova, D. J. Org. Chem. 1997, 62, 5219–5221;
(h) Sato, K.; Bando, T.; Shindo, M.; Shishido, K.
Heterocycles 1999, 50, 11–15; (i) Fuganti, C.; Serra, S. J.
Chem. Soc., Perkin Trans. 1 2000, 3758–3764.
15. Kishuku, H.; Yoshimura, T.; Kakehashi, T.; Shindo, M.;
Shishido, K. Heterocycles 2003, 61, 125–131.
16. Miller, S. L.; Tinto, W. F.; Mclean, S.; Reynolds, W. F.;
Yu, M. J. Nat. Prod. 1995, 58, 1116–1119.
17. Analytical data for helibisabonol A (7): colourless oil;
Rf = 0.16 (PE/Et2O = 1/4); [a]D ꢀ31.5 (c 0.30, MeOH); IR
1
(neat) 3416, 1652, 1452, 1202 cmꢀ1; H NMR (300 MHz,
C3D6O) d 0.97 (3H, s, H-12), 1.15 (3H, s, H-13), 1.18 (3H,
d, J 6.9 Hz, H-15), 1.36–1.49 (2H, m, H-9), 1.60 (1H, m,
H-8), 1.79 (1H, m, H-80), 2.09 (3H, s, H-14), 3.15 (1H,
sext, J 6.9 Hz, H-7), 3.72 (1H, dd, J 4.8, 8.1 Hz, H-10),
6.58 (1H, s, H-3), 6.62 (1H, s, H-6); 13C NMR (75 MHz,
C3D6O) d 14.8 (C-14), 20.8 (C-15), 22.4 (C-12), 25.5 (C-
13), 27.5 (C-9), 31.6 (C-7), 34.3 (C-8), 79.6 (C-11), 83.0 (C-
10), 113.1 (C-6), 117.4 (C-3), 121.8 (C-4), 131.2 (C-1),
147.4 (C-5), 148.4 (C-2).
4. Aguilar, M. I.; Delgado, G.; Villarreal, M. L. Rev. Soc.
Quim. Mex. 2001, 45, 56–59.
´
5. Aguilar, M. I.; Delgado, G.; Hernandez, L.; Villarreal,
M. L. Nat. Prod. Lett. 2001, 15, 93–101.
6. McEnroe, F. J.; Fenical, W. Tetrahedron 1978, 34, 1661–
1664.
´
7. Macıas, F. A.; Torres, A.; Galindo, J. L. G.; Varela, R.
´
M.; Alvarez, J. A.; Molinillo, J. M. G. Phytochemistry
For 7R,10R-(21): white crystals; mp: 64–67 °C; Rf = 0.16
2002, 61, 687–692.
(PE/Et2O = 1/4); IR (neat) 3514, 1638, 1533, 1425,
8. Aguilar, M. I.; Delgado, G.; Bye, R.; Linaress, E.
Phytochemistry 1993, 33, 1161–1163.
1251 cmꢀ1 1H NMR (300 MHz, C3D6O) d 0.98 (3H, s,
;
H-12), 1.16 (3H, d, J 6.9 Hz, H-15), 1.19 (3H, s, H-13),
1.36–1.48 (2H, m, H-9), 1.62–1.79 (2H, m, H-8), 2.09 (3H,
s, H-14), 3.10 (1H, sext, J 6.9 Hz, H-7), 3.66 (1H, dd, J 3.9,
8.7 Hz, H-10), 6.58 (1H, s, H-3), 6.62 (1H, s, H-6); 13C
NMR (75MHz, C3D6O) d 15.0 (C-14), 20.7 (C-15), 22.4
(C-12), 25.5 (C-13), 27.4 (C-8), 34.6 (C-9), 32.1 (C-7), 79.7
(C-11), 83.5 (C-10), 113.0 (C-6), 117.3 (C-3), 121.6 (C-4),
131.1 (C-1), 147.1 (C-5), 148.3 (C-2).
9. Manguro, L. O. A.; Ugi, I.; Lemmen, P. Chem. Pharm.
Bull. 2003, 51, 479–482.
´
10. (a) Sanchez, I. H.; Lemini, C.; Joseph-Nathan, P. J. Org.
Chem. 1981, 46, 4666–4667; (b) Ono, M.; Yamamoto, Y.;
Todoroki, R.; Akita, A. Heterocycles 1994, 37, 181–185;
(c) Ono, M.; Yamamoto, Y.; Akita, H. Chem. Pharm.
Bull. 1995, 43, 553–558; (d) Kad, G. L.; Khurana, A.;
Singh, V.; Singh, J. J. Chem. Res. (S) 1999, 164–165; (e)
Vyvyan, J. R.; Loitz, C.; Looper, R. E.; Mattingly, C. S.;
Peterson, E. A.; Staben, S. T. J. Org. Chem. 2004, 69,
2461–2468.
18. Analytical data for allylic alcohol (9): colourless oil;
Rf = 0.24 (PE/Et2O, 8/2); [a]D ꢀ16.6 (c 1.34, CHCl3); IR
(neat) 3382, 2936, 2868, 1612, 1583, 1500, 1457, 1414,
1255, 1135, 1043, 900, 853, 815 cmꢀ1; 1H NMR (300 MHz,
CDCl3) d 1.25 (3H, d, J 6.9 Hz, H-15), 1.39–1.64 (4H, m,
H-8, H-9), 1.66 (3H, t, J 1.2 Hz, H-13), 2.18 (3H, s, H-14),
2.66 (1H, sext, J 6.9 Hz, H-7), 3.83 (3H, s, –OMe), 4.03
(1H, m, H-10), 4.82 (1H, m, H-12b), 4.91 (1H, m, H-12a),
6.64 (1H, d, J 1.5 Hz, H-2), 6.68 (1H, dd, J 7.5, 1.5 Hz, H-
6), 7.04 (1H, dd, J 7.5, 0.6 Hz, H-5); EIMS m/z 248 (37)
[M+, C16H24O2], 230 (2) [MꢀH2O]+, 205 (4), 189 (5), 175
(4), 162 (100), 149 (100), 135 (47), 123 (41), 117 (19), 105
(16), 91 (51), 84 (6), 77 (20), 71 (26); HREIMS calcd for
C16H24O2 248.1776, found 248.1773.
11. (a) Takabatake, K.; Nishi, I.; Shindo, M.; Shishido, K. J.
Chem. Soc., Perkin Trans. 1 2000, 1807–1808; (b) Yoshi-
mura, T.; Kisyuku, H.; Kamei, T.; Takabatake, K.;
Shindo, M.; Shishido, K. Arkivoc 2003, 8, 247–255.
12. Kolb, H. C.; VanNieuwenhze, M. S.; Sharpless, K. B.
Chem. Rev. 1994, 94, 2483–2547.
13. Ohtani, I.; Kusumi, T.; Kashman, Y.; Kakisawa, H. J.
Am. Chem. Soc. 1991, 113, 4092–4096.
14. Analytical data for (7R,10S)-10,11-dihydro-10,11-dihydr-
oxyxanthorrhizol (2): Rf = 0.29 (PE/Et2O, 1/9); [a]D ꢀ64.7
(c 0.51, MeOH); IR (neat) 3361, 1619, 1589, 1260 cmꢀ1
;
1H NMR (300 MHz, CDCl3) d 1.08 (3 H, s, H-12), 1.15
(3H, s, H-13), 1.18 (1H, m, H-90), 1.23 (3H, d, J 6.9 Hz, H-
15), 1.40 (1H, m, H-9), 1.60 (1H, m, H-80), 1.86 (1H, m, H-
8), 2.21 (3H, s, H-14), 2.64 (1H, sext, J 6.9 Hz, H-7), 3.37
(1H, br d, J 10.2 Hz, H-10), 5.06 (1H, s, OH), 6.62 (1H, d,
J 1.8 Hz, H-2), 6.66 (1H, dd, J 7.8, 1.8 Hz, H-6), 7.02 (1H,
d, J 7.8 Hz, H-5); 13C NMR (75 MHz, CDCl3) d 15.4 (C-
14), 23.0 (C-12), 23.2 (C-15), 26.5 (C-13), 29.6 (C-9), 35.0
(C-8), 39.3 (C-7), 73.3 (C-11), 78.6 (C-10), 113.3 (C-2),
119.4 (C-6), 121.3 (C-4), 130.9 (C-5), 146.4 (C-1), 153.9 (C-
3); EIMS m/z 252 (29) [M+, C15H24O3], 234 (2), 216 (7),
194 (53), 175 (64), 161 (24), 148 (89), 135 (100), 121 (21),
109 (27), 91 (21), 77 (11), 67 (6), 59 (95).
For allylic alcohol (10): colourless oil; Rf = 0.55 (PE/Et2O,
2/3); IR (neat) 3403, 3066, 3030, 2926, 2865, 1649, 1610,
1582, 1510, 1453, 1419, 1378, 1308, 1254, 1161, 1132, 1025,
1
899, 850, 815 cmꢀ1; H NMR (300 MHz, CDCl3) d 1.26
(3H, d, J 6.9 Hz, H-15), 1.42 (2H, m, H-9), 1.58 (2H, m,
H-8), 1.68 (3H, s, H-13), 2.28 (3H, s, H-14), 2.69 (1H, sext,
J 6.9 Hz, H-7), 4.03 (1H, t, J 6 Hz, H-10), 4.84 (1H, m,
H-12b), 4.93 (1H, m, H-12a), 5.12 (2H, s, OCH2Ph), 6.73
(1H, d, J 1.5, H-2), 6.75 (1H, dd, J 1.5, 7.8 Hz, H-6), 7.09
(1H, dd, J 0.6, 7.8 Hz, H-5), 7.32-7.39 (5H, m, C6H5); 13
C
NMR (75 MHz, CDCl3) d 16.0 (C-14), 17.5 (C-13), 22.4
(C-15), 33.0 (C-9), 33.9 (C-8), 30.9 (C-7), 70.3 (OCH2Ph),
75.7 (C-10), 110.8 (C-8), 112.2 (C-12), 119.3 (C-6), 124.7
(C-4), 126.8–128.4 (C-20–C-60), 130.5 (C-5), 137.7 (C-10),
146.4 (C-1), 148.8 (C-11), 157.0 (C-3); HRMS calcd for
C22H28O2 324.2180, found 324.2182.
For (7R,10R)-10,11-dihydro-10,11-dihydroxyxanthorrhi-
zol (3): Rf = 0.29 (PE/Et2O, 1/9); [a]D +3.33 (c 0.30,
MeOH); IR (neat) 3382, 1619, 1589, 1256 cmꢀ1; 1H NMR