S. Baktharaman et al. / Tetrahedron Letters 46 (2005) 7527–7529
7529
O
O
O
1. A, DCC, DMAP,
2. DBU, CHCl3
1. HCOOH, PPh3, DEAD
2. 3N HCl, dioxane
TBSO
TBSO
OH
O
O
O
11a
65%
70%
12b
11b
benzoic acid, TBAF
78%
1b
Scheme 4. Synthesis of 1b.
inversion15a with the acid A gave only 5–10% yields of the
products. An alternative strategy was conceived, where
formic acid was to be used to invert the hydroxyl groups
in 11a and 11c.15b Reaction of the alcohol 11a with for-
mic acid under Mitsunobu condition followed by in situ
hydrolysis of the formate ester provided inverted alcohol
11b easily. Once 11b was in hand, it was transformed into
the final target 1b using a similar sequence of reactions
(Scheme 4). Similarly, the synthesis of 1d was completed
from 11c.
`
Chem. Pharm. Bull. 1990, 38, 2574–2576; (c) Solladie, D.
G.; Gressot-Kempf, L. Tetrahedron: Asymmetry 1996, 7,
2371–2379; (d) Reddy, M. V. R.; Yucel, A. J.; Rama-
chandran, P. V. J. Org. Chem. 2001, 66, 2512–2514; (e)
Garass, S. D.; Hunter, T. J.; OÕDoherty, G. A. J. Org.
Chem. 2002, 67, 2682–2685; (f) Enders, D.; Steinbusch, D.
Eur. J. Org. Chem. 2003, 22, 4450–4454.
6. (a) Raina, S.; Singh, V. K. Tetrahedron 1996, 52, 4479–
4484; (b) Chandrasekhar, M.; Raina, S.; Singh, V. K.
Tetrahedron Lett. 2000, 41, 4969–4971; (c) Chandrase-
khar, M.; Chandra, K. L.; Singh, V. K. J. Org. Chem.
2003, 68, 4039–4045; (d) Raina, S.; Prasad, B. A. B.;
Singh, V. K. Arkivoc 2003, 6, 16–24; (e) Singh, R. P.;
Singh, V. K. J. Org. Chem. 2004, 69, 3425–3430.
7. Larcheveque, M.; Mambu, L.; Petit, Y. Synth. Commun.
1991, 21, 2295–2300.
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3360–3365.
In conclusion, we have accomplished the asymmetric
synthesis of all the four stereoisomers of tarchonanthus-
lactone 1a–d from a common intermediate 6, which was
readily prepared from (R)-3-hydroxy butanoate 7. The
approach involved the use of b,c-unsaturated lactone
obtained via a Kulinkovich reaction followed by a ring
closing metathesis (RCM). The overall yield of the nat-
ural product 1a by our method is 26%, which is higher
than the literature methods.
10. Luche, J. L.; Gernal, A. L. J. Am. Chem. Soc. 1979, 101,
5848–5849.
11. (a) Various reagents, such as DIBALH, at various
temperatures with or without Lewis acid, such as ZnCl2,
Ti(iOPr)4 and BINAL-H, gave poor diastereoselectivity.;
(b) L-Selectride gave the 1,4-reduction product predomi-
nantly.; (c) NaBH4–ZnCl2/MeOH gave 1,4-addition of
MeOH.
Acknowledgements
We thank CSIR for a research Grant to V.K.S. and
research fellowships to S.B. and S.S.
12. (a) Noyori, R.; Tomino, I.; Tanimoto, Y.; Nishizawa, M.
J. Am. Chem. Soc. 1984, 106, 6708–6716; (b) Noyori, R.;
Tomino, I.; Yamada, M.; Nishizawa, M. J. Am. Chem.
References and notes
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