Synthesis of both enantiomers of halitunal

Tetrahedron Letters

Volumn 37, Issue 13, 1996, Pages 2253-2256

  Shimano, Kazunori ^a   Ge, Yuting ^a   Sakaguchi, Kazuhiko ^a   Isoe, Sachihiko ^a  

^a Osaka Prefecture University   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

DITERPENE; HALITUNAL; UNCLASSIFIED DRUG;

ARTICLE; DRUG SYNTHESIS; ENANTIOMER; NUCLEAR MAGNETIC RESONANCE; REACTION ANALYSIS;

EID: 0029940062     PISSN: 00404039     EISSN: None     Source Type: Journal    
DOI: 10.1016/0040-4039(96)00268-7     Document Type: Article

References (14)

1. Koehn, F. E.; Gunasekara, S. P.; Niel, D. N.; Cross, S. S. Tetrahedron Lett. 1991, 32, 169.
2. Isoe, S.; Katsumura, S.; Okada, T.; Yamamoto, K.; Takemoto, T.; Inaba, H.; Han, Q.; Nakatani, K. Tetrahedron Lett. 1987, 28, 5865.
3. Isoe, S; Ge, Y.; Yamamoto, K.; Katsumura, S. Tetrahedron Lett. 1988, 29, 4591.
4. Ge, Y.; Isoe, S. Chem. Lett. 1992, 139.
5. Nakatani, K.; Hiraishi, A.; Han, Q.; Isoe, S. Bull. Chem. Soc. Jpn. 1993, 66, 2646.
6. Ge, Y.; Kondo, S.; Katsumura, S.; Nakatani, K.; Isoe, S. Tetrahedron 1993, 49, 10555.
7. Gao, Y.; Hanson, R. M.; Klunder, J. M.; Ko, S. Y.; Masamune, H.; Sharpless, K. B. J. Am. Chem. Soc. 1987, 109, 5765.
8. (a) Stork, G.; Maldonado, L. J. Am. Chem. Soc. 1971, 93, 5286.
9. (b) Albright, J. D. Tetrahedron 1983, 39, 3207. The compound 14 was prepared by (1) cyanosilylation of the geranyl aldehyde (13) with trimethylsilylcyanide (TMSCN) followed by KCN and 18-crown-6, and (2) exchange of the resulting silyl group to the ethoxyethyl group with pyridinium p-toluenesulfonate (PPTS) in excellent yield. equation presented
10. 3) δ 6.21 (s, 1 H), 5.77 (s, 1 H), 5.16 (d, 1 H, J= 8.6 Hz), 5.08 (m, 1 H), 4.69 (d, 1 H, J = 8.5 Hz), 4.45 (q, J = 6.7 Hz, 1 H), 4.28 (s, 2 H), 2.82 (q, 1 H, J = 8.5 Hz), 2.67 (m, 1 H), 2.55 (ddd, J = 8.5, 8.5, 1.4 Hz, 1 H), 2.31-1.97 (7 H), 1.68 (s, 3 H), 1.67 (s, 3 H), 1.60 (s, 3 H), 0.92 (s, 9 H), 0.15 (s, 3 H), 0.13 (s, 3 H).
11. 3) δ 6.20 (s, 1 H), 5.76 (s, 1 H), 5.05 (m, 1 H), 4.66 (d, 1 H, J = 7.9 Hz), 4.36 (m, 1 H), 4.19 (m, 1 H), 3.56 (dd, 1 H, J = 14.0, 7.3 Hz), 2.79 (m, 1 H), 2.67 (d, 1 H, J = 7.3 Hz), 2.61 (m, 1 H), 2.52 (m, 1 H), 2.38 (dd, 1 H, J = 7.5, 1.4 Hz), 2.26 (dd, 1 H, J = 14.7, 7.3 Hz), 2.15 - 1.94 (6 H), 1.66 (s, 3 H), 1.59 (s, 3 H), 0.89 (s, 21 H), 0.89 (s, 3 H), 0.08 (s, 3 H), 0.05 (s, 3 H), 0.04 (s, 3 H).
12. As shown in Table 1, the signs of the Δδ values clearly indicate the absolute configuration at C12 of 9b to be S, which was in good agreement with the empirical rule reported by Kusumi, et al. Ohtani, I.; Kusumi, T.; Kashman, Y.; Kakisawa, H. J. Am. Chem. Soc. 1991, 113, 4092. equation presented
13. max (c = 0.005, MeOH) (Δε) 257.4 (-1.39), 227.6 (+4.53) nm.
14. 12