648
R. Murashige et al. / Tetrahedron 67 (2011) 641e649
48.7, 39.3; HRMS (ESI): MHþ, found 320.0751. C13H13F3NO5 requires
320.0746; [
D þ75.0 (c 1.0, CHCl3).
Compound (S)-14: 38%; nmax (neat) 3300, 1720, 1640,
1580 cmꢂ1
dH (500 MHz, CDCl3) 7.70 (1H, d, J 8.0 Hz), 7.53 (1H, t, J
H2O¼4:1:1) to afford (S)-17 as colorless amorphous mass (0.103 g,
90%).
a
]
Compound (S)-17: nmax (neat) 3100, 1740 cmꢂ1; mp 217e220 ꢀC;
dH (500 MHz, CD3OD) 7.06 (2H, d, J 8.6 Hz), 6.73 (2H, d, J 8.6 Hz),
3.95 (1H, t, J 6.3 Hz), 2.75e2.63 (2H, m), 2.22e2.18 (1H, m),
2.13e2.06 (1H, m); dC (125 MHz, CD3OD) 171.78, 157.05, 131.90,
130.36, 116.41, 53.44, 33.92, 31.23; HRMS (ESI): MHþ, found
;
8.0 Hz), 7.44 (1H, d, J 6.9 Hz), 7.01 (1H, d, J 8.6 Hz), 6.95 (1H, t,
J¼7.4 Hz), 4.96 (1H, m), 3.90 (1H, dd, J 18.3, 4.0 Hz), 3.81 (3H, s),
3.68 (1H, dd, J 18.3, 4.0 Hz); dC (125 MHz, CDCl3) 202.56, 169.72,
2
162.45, 156.98 (q, JCF 38.0 Hz), 137.49, 129.80, 119.44, 118.75,
196.0958. C10H14NO3 requires 196.0974; [
a
]
þ35.6 (c 1.0, CHCl3);
D
1
118.59, 115.50 (q, JCF 287.5 Hz), 53.32, 48.29, 39.41; HRMS (ESI):
chiral HPLC tR¼6.78 min.
MHþ, found 320.0749. C13H13F3NO5 requires 320.0746; [
(c 1.0, CHCl3).
a
]D þ107.0
Compound (S)-18: 95%; nmax (neat) 3350, 3100, 1750 cmꢂ1; mp
194e196 ꢀC; dH (500 MHz, CD3OH) 7.11 (1H, d, J 7.4 Hz), 7.06 (1H, t, J
7.7 Hz), 6.80e6.77 (2H, m), 3.91 (1H, t, J 6.3 Hz), 2.85e2.82 (1H, m),
2.75e2.69 (1H, m), 2.27e2.10 (2H, m); dC (125 MHz, CD3OD) 172.82,
157.21, 132.16, 129.77, 128.20, 121.78, 116.90, 54.55, 32.96, 27.77;
Compounds (R)-13 and (R)-14 were prepared in an identical
manner as described above starting from(R)-11. The dH and dC data
for these samples were identical with these recorded for (S)-13 and
(S)-14.
[a
]
D þ27.3 (c 1.0, CHCl3); chiral HPLC tR¼7.34 min.
Compound (R)-13: 40%; [
Compound (R)-14: 39%; [
a
a
]
]
D ꢂ74.0 (c 1.0, CHCl3).
Compounds (R)-17 and (R)-18: The dH and dC NMR for these
D ꢂ108.0 (c 1.0, CHCl3).
samples were identical with these recorded for (S)-17 and (S)-18.
Compound (R)-17: 97%; [
a
]
ꢂ34.5 (c 1.0, 1 N HCl); chiral HPLC
D
4.5.3. General procedure of Fries rearrangement in TfOH. Compound
(S)-12 (1.008 g, 3.15 mmol) was dissolved in TfOH (5 ml) at 0 ꢀC and
warmed to room temperature. The reaction mixture was stirred for
16 h and poured into cold water and ethyl acetate. The organic layer
was treated in the same manner as described for FriedeleCrafts
reaction to afford (S)-13 (0.483 g, 48%) and (S)-14 (0.360 g, 36%).
Analytical data of each isomer were identical with the Friedele
Crafts products.
Compounds (R)-13 and (R)-14 were prepared in an identical
manner as described above starting from (R)-12 ((R)-13 45%, (R)-14
33%). Analytical data of each isomer were identical with the Frie-
deleCrafts products.
tR¼8.59 min. Compound (R)-18: 96%; [
a
]
ꢂ29.5 (c 1.0, 1 N HCl);
D
chiral HPLC tR¼9.35 min.
Acknowledgements
We are very grateful to Professor G.D. Holman (University of
Bath, U.K.) for valuable advice throughout the manuscript. This
research was partially supported by Ministry of Education, Science,
Sports and Culture Grant-in-Aid for Scientific Research on a Priority
Area, 18032007, for Scientific Research on Innovative Areas,
20200038 and for Scientific Research (C), 19510210, 21510219.
Supplementary data
4.5.4. General procedure for benzylic carbonyl reduction. Compound
(S)-13 (0.170 g, 0.53 mmol) and Pd/C (10%, 30 mg) were suspended
in acetic acid (10 ml). The reaction mixture was stirred under hy-
drogen atmosphere for an hour, and then filtrated with Celite. The
filtrate was concentrated and the residue was subjected to silica
column chromatography (ethyl acetate/hexane¼1:2) to afford (S)-
15 as amorphous mass (0.157 g, 97%).
Supplementary data associated with this article can be found in
References and notes
1. (a) Martin, R. Org. Prep. Proced. Int. 1992, 24, 369e435; (b) Olah, G. A. Frie-
deleCrafts and Related Reactions; Wiley-Interscience: New York, NY and London,
1963e1964; Vols. IeIV.
Compound (S)-15: nmax (neat) 3350, 1720, 1595 cmꢂ1
; dH
(500 MHz, CDCl3) 7.03 (2H, d, J 8.6 Hz), 6.83 (1H, d, J 6.3 Hz), 6.77
(2H, d, J 8.6 Hz), 4.67e4.64 (1H, m), 3.77 (3H, s), 2.61e2.58 (2H, m),
2.27e2.24 (1H, m), 2.12e2.05 (1H, m); dC (125 MHz, CDCl3) 171.40,
2. Olah, G. A.; Prahash, G. K. S.; Sommer, J. Superacids; Wiley: New York, NY, 1985.
3. Olah, G. A.; Prahash, G. K. S.; Sommer, J. Science 1979, 206, 13e20.
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2227e2302.
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6566e6568; (b) Murai, Y.; Hatanaka, Y.; Kanaoka, Y.; Hashimoto, M. Heterocy-
cles 2009, 79, 359e364; (c) Murashige, R.; Murai, Y.; Hatanaka, Y.; Hashimoto,
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9. Evans, W. C.; Walker, N. J. Chem. Soc. 1947, 1571e1573.
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2
1
156.90 (q, JCF 37.6 Hz), 154.29, 131.58, 129.41, 115.53 (q, JCF
287.9 Hz), 115.45, 52.96, 52.37, 33.33, 30.39; HRMS (ESI): MHþ,
found 306.0960. C13H15F3NO4 requires 306.0953; [
CHCl3).
a
]D þ39.0 (c 1.0,
Compound (S)-16 was obtained from (S)-14 in the same manner
as (S)-13.
Compound (S)-16: 86%; nmax (neat) 3320, 1720, 1550 cmꢂ1
;
dH
(500 MHz, CDCl3) 7.23 (1H, d, J 6.9 Hz), 7.10e7.09 (2H, m), 6.88 (1H,
t, J 7.4 Hz), 6.74 (1H, d, J 8.0 Hz), 4.67e4.66 (1H, m), 3.68 (3H, s),
2.72e2.67 (2H, m), 2.35e2.26 (1H, m), 2.19e2.16 (1H, m); dC
11. Yamada, M.; Nagashima, N.; Hasegawa, J.; Takahashi, S. Tetrahedron Lett. 1998,
39, 9019e9022.
2
(125 MHz, CDCl3) 171.38, 157.12 (q, JCF 37.6 Hz), 153.52, 130.52,
127.93, 126.11, 120.97, 115.68 (q, 1JCF 287.5 Hz), 115.45, 52.87, 52.37,
12. Xie, Y.; Lou, R.; Li, Z.; Mi, A.; Jiang, Y. Tetrahedron: Asymmetry 2000, 11,
1487e1494.
31.35, 25.36; [
a
]
D þ44.0 (c 1.0, CHCl3).
ꢀ
13. Brea, R. J.; Lopez-Deber, M. P.; Castedo, L.; Granja, J. R. J. Org. Chem. 2006, 71,
Compounds (R)-15 and (R)-16 were prepared in an identical
manner as described above starting from corresponding pre-
cursors. The dH and dC for these samples were identical with these
recorded for (S)-15 and (S)-16.
7870e7873.
14. (a) Reifenrath, W. G.; Bertelli, D. J.; Micklus, M. J.; Fries, D. S. Tetrahedron Lett.
1976, 17, 1959e1962; (b) Nordlander, J. E.; Payne, M. J.; Njoroge, F. G.; Vish-
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A. W.; Colleluori, J. R. J. Org. Chem. 1987, 52, 5143e5150; (d) Griesbeck, A. G.;
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Compound (R)-15: 99%; [
Compound (R)-16: 87%; [
a
a
]
]
D ꢂ38.5 (c 1.0, CHCl3).
D ꢂ44.0 (c 1.0, CHCl3).
ꢀ
15. Dumeunier, R.; Marko, I. E. Tetrahedron Lett. 2004, 45, 825e829.
4.5.5. General procedure for deprotection. Compound (S)-15
(0.152 g, 0.50 mmol) was dissolved in 6 M HCl (2 ml). The reaction
mixture was heated at 80 ꢀC for 6 h, then concentrated. The residue
was subjected to silica column chromatography (CH3CN/MeOH/
16. Kobayashi, S.; Moriwaki, M.; Hachiya, I. Tetrahedron Lett. 1996, 37, 2053e2056.
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