6896
Y. O. Ko et al. / Tetrahedron Letters 51 (2010) 6893–6896
Kitajima, M.; Kogure, N.; Nonato, M. G.; Takayama, H. J. Nat. Prod. 2010, 73,
1453.
ring-opening reaction with the Blaise reaction intermediate, where
the regioselectivity of epoxide ring-opening was largely deter-
mined by the steric and electronic nature of epoxide. A modifica-
tion of the addition of a stoichiometric amount of n-BuLi to the
Blaise reaction intermediate increased its reactivity toward the
5. Selected paper, see: (a) Movassaghi, M.; Jacobsen, E. N. J. Am. Chem. Soc. 2002,
124, 2456; (b) Gutierrez, J. L. G.; Jimenez-Cruz, F.; Epinosa, N. R. Tetrahedron
Lett. 2005, 46, 803; (c) Cho, C. S.; Shim, H. S. Tetrahedron Lett. 2006, 47, 3835; (d)
Dias, L. C.; de Castro, I. B. D.; Steil, L. J.; Augusto, T. Tetrahedron Lett. 2006, 47,
213; (e) Capuzzi, M.; Gambacotrta, A.; Gasperi, T.; Loreto, M. A.; Tardella, P. A.
Eur. J. Org. Chem. 2006, 5076; (f) Dohi, T.; Takenaga, N.; Goto, A.; Maruyama, A.;
Kita, Y. Org. Lett. 2007, 9, 3129; (g) Ramachandran, P. V.; Garrett, G.; Pratihar, D.
Org. Lett. 2007, 9, 4753; (h) Malkov, A. V.; Friscourt, F.; Bell, M.; Swarbrick, M.
epoxide opening reaction and lactonization to provide
a-(aminom-
ethylene)- -lactones efficiently. Further applications of the Blaise
c
reaction intermediate to other conceivable reactions are underway
and will be reported in due course.
ˇ
´
E.; Kocovsky, P. J. Org. Chem. 2008, 73, 3996; (i) Park, H. S.; Kwon, D. W.; Lee, K.;
Kim, Y. H. Tetrahedron Lett. 2008, 49, 1616.
6. (a) Taylor, S. K. Tetrahedron 2000, 56, 1149. and references therein; (b)
Domingo, L. R.; Gil, S.; Parra, M.; Segura, J. Molecules 2008, 13, 1303.
7. Takaya, H.; Ito, M.; Murahashi, S.-I. J. Am. Chem. Soc. 2009, 131, 10824.
8. When the reaction mixture was workedup with 3 N aqueous HCl solution, the
Acknowledgments
This work was supported by the Korea Research Foundation
(KRF-20090070898 and KRF-20090063004), the Seoul R&D fellow-
ship for Y. O. Ko, and RP-supporting from Ewha Womans Univer-
sity for Y. S. Chun.
a
-benzoylated b-phenyl-
previously reported that reaction of ethyl acetoacetate with styrene oxide in
the presence of sodium ethoxide afforded a mixture of b-phenyl- and -phenyl
substituted -acetyl- -butyrolactones in 45% and 55% yield, respectively, see:
Reitz, D. B. J. Org. Chem. 1979, 44, 4707.
9. Typical experimental procedure: to a stirred suspension of zinc dust (Aldrich,
10 m, 1.0 g, 15.3 mmol) was added 6 mol % of methanesulfonic acid in
c-butyrolactone was isolated in 68% yield. It has been
c
a
c
l
Supplementary data
anhydrous THF (2.5 mL). After 10 min reflux, benzonitrile 1a (0.8 mL,
7.6 mmol) was added. While maintaining reflux temperature, ethyl
bromoacetate (1.26 mL, 11.4 mmol) was added over 1 h by using a syringe
pump, and the reaction mixture was refluxed for 1 h. The reaction mixture was
cooled to 0 °C, and an equivalent amount of n-BuLi (4.75 mL of 1.6 M in hexane
solution, 7.6 mmol) was added at 0 °C. The 3.0 M solution of styrene oxide
(1.05 mL, 7.6 mmol) in THF was added slowly for 12 h at 45 °C. The reaction
was quenched with aqueous satd NH4Cl solution at room temperature, and
extracted with ethyl acetate (3 ꢀ 20 mL). The combined organic layer was dried
with MgSO4, filtered, and concentrated. The residue was purified by silica
chromatography to afford 3a (1.41 g, 70%).
Supplementary data associated with this article can be found, in
References and notes
1. (a) Ho, T.-L. Tandem Organic Reactions; Wiley: New York, 1992; (b) Tietze, L. F.;
Brasche, G.; Gericke, K. Domino Reactions in Organic Synthesis; Wiley-VCH:
Weinheim, 2006; (c) Nicolaou, K. C.; Edmonds, D. J.; Bulger, P. G. Angew. Chem.,
Int. Ed. 2006, 45, 7134; (d) Fürstner, A. Angew. Chem., Int. Ed. 2009, 48, 1364; (e)
Parsons, P. J.; Penkett, C. S.; Shell, A. J. Chem. Rev. 1996, 96, 195.
2. (a) Blaise, E. E. C. R. Hebd. Seances Acad. Sci. 1901, 132, 478; (b) Blaise, E. E. C. R.
Hebd. Seances Acad. Sci. 1901, 132, 987; (c) Rathke, M. W.; Weipert, P. In Zinc
Enolates: The Reformatsky and Blaise Reaction in Comprehensive Organic
Reactions; Trost, B. M., Ed.; Pergamon: Oxford, 1991; Vol. 2, pp 277–299; (d)
Rao, H. S. P.; Rafi, S.; Padmavathy, K. Tetrahedron 2008, 64, 8037.
3. (a) Chun, Y. S.; Lee, K. K.; Ko, Y. O.; Shin, H.; Lee, S.-g. Chem. Commun. 2008,
5098; (b) Ko, Y. O.; Chun, Y. S.; Park, C.-L.; Kim, Y.; Shin, H.; Ahn, S.; Hong, J.;
Lee, S.-g. Org. Biomol. Chem. 2009, 7, 1132; (c) Chun, Y. S.; Ko, Y. O.; Shin, H.; Lee,
S.-g. Org. Lett. 2009, 11, 3414; (d) Chun, Y. S.; Ryu, K. Y.; Ko, Y. O.; Hong, J. Y.;
Hong, J.; Shin, H.; Lee, S.-g. J. Org. Chem. 2009, 74, 7556.
4. Selected papers, see: (a) Zhang, S.; Won, Y.-K.; Ong, C.-N.; Shen, H.-M. Curr.
Med. Chem. 2005, 5, 239; (b) González, A. G.; Silva, M. H.; Padrón, J. I.; León, F.;
Reyes, E.; Álvarez-Mon, M.; Pivel, J. P.; Quintana, J.; Estévez, F.; Bermejo, J. J.
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2009, 65, 221; (e) Ata, A.; Betteridge, J.; Schaub, E.; Kozera, D. J.; Holloway, P.;
Samerasekera, R. Chem. Biodivers. 2009, 6, 1453; (f) Oliver, C. M.; Schaefer, A. L.;
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10. Crystal data for 3a (CIF deposition number: CCDC793437):
C17H15NO2,
momoclinic, P21/c, a = 6.0057(9) Å, b = 10.3248(15) Å, c = 22.742(3) Å,
V = 1407.8(4) Å3, Z = 4, Dc = 1.252 g/m3, F(0 0 0) = 560,7721 independent
collections with I/2
crystallographic analysis were measured on
diffractometer using graphite-monochromate Mo KR (k 0.71073 Å) and
scans in the range of h, 1.79 < h < 26.00. Crystal data for 3d (CIF deposition
number: CCDC 793438): 17H14FNO2, momoclinic, P21/c, a = 13.707(3) Å,
b = 9.6840(19) Å, c = 11.622(2) Å, V = 1437.9(5) Å3, Z = 4, Dc = 1.309 g/m3,
F(0 0 0) = 592,7634 independent collections with I/2 (I) (R1 = 0.0560,
wR2 = 0.1453), GOF (F2) = 0.945 data for crystallographic analysis were
measured on Bruker SMART APX diffractometer using graphite-
monochromate Mo KR (k 0.71073 Å) and -2 scans in the range of h,
1.59 < h < 26.00. Structure was solved and refined by using the SHEL V6.12.
11. Crystal data for 4a (CIF deposition number: CCDC 793436): 18H17NO3,
r
(I) (R1 = 0.0366, wR2 = 0.0531), GOF (F2) = 0.600 data for
a
Bruker SMART APX
-2
x
C
r
a
x
C
momoclinic, P21/c, a = 12.320(2) Å, b = 10.1168(16) Å, c = 12.1529(19) Å,
V = 1512.8(4) Å3, Z = 4, Dc = 1.297 g/m3, F(0 0 0) = 624,7619 independent
collections with I/2
crystallographic analysis were measured on
diffractometer using graphite-monochromate Mo KR (k 0.71073 Å) and
r
(I) (R1 = 0.0566, wR2 = 0.1605), GOF (F2) = 1.062 data for
a
Bruker SMART APX
-2
x
scans in the range of h, 2.61 < h < 26.00. Structure was solved and refined by
using the SHEL V6.12.