Professional Documents
Culture Documents
Samarium-Mediated Barbier Reaction of CA
Samarium-Mediated Barbier Reaction of CA
LETTERS
Pergamon Tetrahedron Letters 42 (2001) 187 – 189
Abstract— Samarium metal in the presence of catalytic amounts of iodine was found to be effective for the Barbier reaction of
carbonyl compounds. © 2000 Elsevier Science Ltd. All rights reserved.
0040-4039/01/$ - see front matter © 2000 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 0 - 4 0 3 9 ( 0 0 ) 0 1 9 6 1 - 4
188 M. K. Basu, B. K. Banik / Tetrahedron Letters 42 (2001) 187–189
Table 1. Barbier reaction of aldehydes and ketones in the presence of samarium metal and catalytic amounts of iodine in
THF
O HO H
2 Br 20 70
H
Br Br
O OH
O Br a
3 20 70
OMe
O OH
H
4 Br H 20 90
O HO
5 Br 120 20
+
HO
40
HO
O
6 Br 30 64
OH
O
7 Br 30 52
OH
O
8 Br 30 52
OH
O
9 Br 30 56
Br OH
10 CH3(CH2)8CHO 20 81
CH3(CH2)8CH
O I OH
11 20 31
O I OH
12 20 42
O HO
I
13 20 45
a: A mixture of trans-allyl ether and cis-allyl ether (60:40) was obtained (For a related
study, see: Yasuda, M.; Fujibayashi, T.; Baba, A. J. Org. Chem. 1998, 63, 6401).
ever, an isomerization of the double bond was noted required freshly-distilled silyl chloride and a reflux tem-
when homoallyl bromide was used as the halide. perature. In contrast, our method has a much wider
application, requires only samarium and catalytic
Samarium metal was used previously for the Barbier amounts of iodine and can be carried out at room
reaction in the presence of trimethyl silyl bromide and temperature.
trimethyl silyl chloride – sodium iodide with a single
substrate.13 The reactive species was claimed to be Recently, a trivalent samarium cation was proposed to
bivalent samarium cation, although no justification was be the reactive species when imines were allylated or
provided and the structure of the bivalent samarium alkylated by samarium metal and catalytic amounts of
equivalent was not confirmed. In addition, this method iodine.14 The yield of the desired product from the
M. K. Basu, B. K. Banik / Tetrahedron Letters 42 (2001) 187–189 189
reaction of imines and benzyl bromide was low and 3. For example, see: Marton, D.; Stivanello, D.; Tagliavini,
dibenzyl was found to be the major product from the G. J. Org. Chem. 1996, 61, 2731
reaction.15 However, addition of benzyl bromide to the 4. (a) Barbot, F.; Miginiac, P. Tetrahedron Lett. 1975, 44,
ketones by following our method afforded the benzyl 3829. (b) Bernardon, C.; Deberly, A. J. Org. Chem. 1982,
alcohol in an excellent yield, a small portion of which 47, 463.
was dimerized (entries 6 – 10). Thus, the involvement of 5. Katritzky, A. R.; Shobana, N.; Harris, P. A.
trivalent samarium species in this type of addition Organometallics 19
reactions remains a question. Our study indicates that 92, 11, 1381 and references cited therein.
pre-generated bivalent or trivalent samarium species is 6. Li, C.-J.; Chan, T.-H. Tetrahedron 1999, 55, 11149 and
not required for the Barbier addition of halides to references cited therein.
carbonyl compounds. We believe the formation of an 7. (a) Girard, P.; Namy, J. L.; Kagan, H. B. J. Am. Chem.
activated samarium-R reagent attacks the carbonyl Soc. 1980, 102, 2693. (b) Soupe, J.; Namy, J. L.; Kagan,
group in THF solution. Further studies are needed to H. B. Tetrahedron Lett. 1982, 23, 3497.
define the critical role of solvents in the samarium- 8. (a) Murakami, M.; Hayashi, M.; Ito, Y. Synlett 1994,
induced addition and dimerization of carbonyl com- 179. (b) Ogawa, A.; Takeuchi, H.; Hirao, T. Tetrahedron
pounds in the presence of halides. Lett. 1999, 40, 7113.
9. Yanada, R.; Negoro, N.; Okaniwa, M.; Ibuka, T. Tetra-
In comparison to all of the previous reports, the present hedron 1999, 55, 13947 and references cited therein.
10. (a) Banik, B. K.; Mukhopadhyay, C.; Venkatraman, M.
method is rapid, convenient and cost-saving. In conclu-
S.; becker, F. F. Tetrahedron Lett. 1998, 39, 7243. (b)
sion, we have demonstrated a general method for Bar-
Basu, M.; Becker, F. F.; Banik, B. K. Tetrahedron Lett.
bier-type addition reactions of aldehydes and ketones in
2000, 41, 5603
excellent yields at room temperature.16
11. Banik, B. K.; Zegrocka, O.; Banik, I.; Hackfeld, L.;
Becker, F. F. Tetrahedron Lett. 1999, 40, 6731.
12. Ghatak, A.; Becker, F. F.; Banik, B. K. Tetrahedron Lett.
Acknowledgements 2000, 41, 3793.
13. Akane, N.; Hatano, T.; Kusui, H.; Nishiyama, Y.; Ishii,
Y. J. Org. Chem. 1994, 59, 7902.
This work was supported in part by a grant received 14. Negoro, N.; Yanada, R.; Okaniwa, M.; Yanada, K.;
from the Robert J. Kleberg Jr. and Helen C. Kleberg Fujita, T. Synlett 1998, 835.
Foundation and an NIH Cancer Center Support Grant, 15. Yanada, R.; Negoro, N.; Okaniwa, M.; Ibuka, T. Tetra-
5-P30-CA16672-25, in particular the shared resources hedron 1999, 55, 13947.
of the Pharmacology and Analytic Center Facility. 16. Typical procedure: Alkyl halide (1.50 mmol) was added
dropwise to samarium (1.50 mmol) (preactivated by heat-
ing with 0.05 mmol of iodine) in 4.0 mL dry THF under
an argon atmosphere at room temperature. A dark blue
References or purple color was generated within 2 – 5 min. The
carbonyl compound (0.5 mmol) was added dropwise
1. For example, see: Yi, X.-H.; Meng, Y.; Hua, X.-G.; Li, while slowly maintaining the blue color of the reaction
C.-J. J. Org. Chem. 1998, 63, 7472 and references cited mixture. The reaction mixture was stirred for 10–30 min
therein. and then was quenched with 0.1N hydrochloric acid. The
2. (a) Mukaiyama, T.; Harada, T. Chem. Lett. 1981, 1527. resulting mixtures were extracted with CH2Cl2, dried over
(b) Wu, S. H.; Huang, B. Z.; Gao, X. Synth. Commun. sodium sulfate and evaporated to dryness. Finally, the
1990, 20, 1279. product was purified by column chromatography.