2
86
C.-C. Chang et al.
LETTER
in water at 30 °C. From the anion study, it is quite clear
that the property of metal ions changes dramatically by
the surrounding anions. At present, the activities of metal
salts associated with a tetrakis(3,5-trifluoromethyl-
phenyl)borate anion in other reactions are currently under
investigation.
(C), 134.4 (C), 129.9 (CH), 129.2 (CH), 39.0 (CH
2
), 26.2
(
4
CH ), 14.2 (CH ).
2 3
-(tert-Butyldimethylsilyloxymethyl)benzaldehyde:22 1H
NMR (300 MHz, CDCl ): d = 10.01 (s, 1 H), 7.85 (d, J = 8
3
Hz, 2 H), 7.49 (d, J = 8 Hz, 2 H), 4.82 (s, 2 H), 0.96 (s, 9 H),
13
0
1
2
4
.13 (s, 6 H). C NMR (100 MHz, CDCl ): d = 191.6 (CH),
3
48.6 (C), 135.3 (C), 129.9 (CH), 126.3 (CH), 65.0 (CH2),
6.7 (CH ), 19.3 (C), –4.3 (CH ).
3
3
-Hydroxymethylbenzaldehyde:23 1H NMR (400 MHz,
Acknowledgment
CDCl ): d = 9.96 (s, 1 H), 7.84 (d, J = 6.8 Hz, 2 H), 7.50 (d,
3
1
3
J = 6.8 Hz, 2 H), 4.78 (s, 2 H). C NMR (100 MHz, CDCl ):
This research was supported by the National Science Council
3
d = 191.7 (CH), 147.7 (C), 135.6 (C), 130.1 (CH), 127.0
(
NSC95-2119-M002-038), Taiwan.
(
3
CH), 65.1 (CH2).
-Ethoxypropionaldehyde: 4 1H NMR (400 MHz, CDCl3):
2
References and Notes
d = 9.78 (t, J = 2 Hz, 1 H), 3.76 (t, J = 6.4 Hz, 2 H), 3.50 (q,
J = 6.8 Hz, 2 H), 2.67 (td, J = 1.6, 6 Hz, 2 H), 1.20 (t, J = 6.4
(1) Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic
Synthesis, 3rd ed.; John Wiley: New York, 1999.
13
Hz, 3 H). C NMR (100 MHz, CDCl ): d = 200.9 (CH), 67.1
3
(
CH ), 64.6 (CH ), 64.6 (CH ), 44.6 (CH ), 16.0 (CH ).
Methyl 4-Formylbenzoate: H NMR (400 MHz, CDCl3):
2
2
2
25 1
2
3
(
2) Recent reviews: (a) Kocienski, P. J. Chem. Soc., Perkin
Trans. 1 2001, 2109. (b) Sartori, G.; Ballini, R.; Bigi, F.;
Bosica, G.; Maggi, R.; Righi, P. Chem. Rev. 2004, 104, 199.
3) Markó, I. E.; Ates, A.; Gautier, A.; Leroy, B.; Plancher, J.
M.; Quesnel, Y.; Vanherck, J. C. Angew. Chem. Int. Ed.
d = 10.09 (s, 1 H), 8.18 (d, J = 8 Hz, 2 H), 7.94 (d, J = 8 Hz,
13
2
(
(
H), 3.95 (s, 3 H). C NMR (100 MHz, CDCl ): d = 191.6
3
(
CH), 166.0 (C), 139.1 (C), 135.1 (C), 130.2 (CH), 129.5
CH), 52.6 (CH3).
1
999, 38, 3207.
4) Bhattacharjya, A.; Majumdar, S. J. Org. Chem. 1999, 64,
682.
5) Yutaka, U.; Koumoto, N.; Fujisawa, T. Chem. Lett. 1989,
623.
(
15) Acetals 1, 6, 7, 8, 9, 10, 11, 15, 17, 18 and 19 were
synthesized according to the literature methods. Other
acetals were obtained from commercial sources:
(
(
5
(a) Compound 1: Mosca, R.; Fagnoni, M.; Mella, M.; Albini,
1
A. Tetrahedron 2001, 57, 10319. (b) Compounds 6 and 7:
Barluenga, J.; del Pozo, C.; Olano, B. Synthesis 1995, 1529.
(
(
6) Ji, H. B. Eur. J. Org. Chem. 2003, 3659.
7) Carrigan, M. D.; Sarapa, D.; Smith, R. C.; Wieland, L. C.;
Mohan, R. S. J. Org. Chem. 2002, 67, 1027.
(
c) Compound 8: Eash, K. J.; Pulia, M. S.; Wieland, L. C.;
Mohan, R. S. J. Org. Chem. 2000, 65, 8399. (d) Compound
: Walton, R.; Lahti, P. M. Synth. Commun. 1998, 28, 1087.
e) Compound 10: Bořkovec, A. B. J. Org. Chem. 1961, 26,
866. (f) Compound 11: Sulzbacher, M.; Bergmann, E.;
Pariser, E. R. J. Am. Chem. Soc. 1948, 70, 2827.
g) Compound 15: Goud, P. M.; Venkatachalam, T. K.;
Uckun, F. M. Synth. Commun. 2003, 33, 1185.
h) Compound 17: Ouchi, M.; Inoue, Y.; Wada, K.; Iketani,
S.; Hakushi, T.; Weber, E. J. Org. Chem. 1987, 52, 2420.
i) Compound 18: Carroll, F. I.; Berrang, B. D.; Linn, C. P.
(
8) (a) Dalpozzo, R.; De Nino, A.; Maiuolo, L.; Procopio, A.;
Tagarelli, A.; Sindona, G.; Bartoli, G. J. Org. Chem. 2002,
9
(
4
67, 9093. (b) Fujioka, H.; Okitsu, T.; Sawama, Y.; Murata,
N.; Li, R.; Kita, Y. J. Am. Chem. Soc. 2006, 128, 5930.
(9) Lipshutz, B. H.; Harvey, D. F. Synth. Commun. 1982, 12,
(
267.
(
(
10) Manabe, K.; Kobayashi, S. Org. Lett. 1999, 1, 1965.
11) Chang, C.-T.; Chen, C.-L.; Liu, Y.-H.; Peng, S.-M.; Chou,
P.-T.; Liu, S.-T. Inorg. Chem. 2006, 45, 7590.
(
(
(
(
12) Akiyama, T.; Matsuda, K.; Fuchibe, K. Synlett 2005, 322.
13) Typical Procedure for Hydrolysis: A mixture of
J. Heterocycl. Chem. 1981, 18, 941. (j) Compound 10: Lai,
J.-Y.; Shi, X.-X.; Dai, L.-X. J. Org. Chem. 1992, 57, 3485.
F
–3
11
NaBAr ×2H O (5 × 10 mmol) and acetal (5.0 mmol) in
4
2
(16) Preparation of 20: A solution of 17 (0.32 g, 2 mmol) and
H O (10 mL) was placed in a 25-mL flask. The resulting
2
Et N (0.38 mL, 2.8 mmol) in anhyd CH Cl (5 mL) was
3
2
2
suspension was stirred vigorously at 30 °C for a certain
period as shown in Table 2. After the completion of the
reaction, the reaction mixture was extracted with CH Cl
cooled in an ice-water bath under dried nitrogen.
Chlorotrimethylsilane (0.31 mL, 2.4 mmol) was slowly
added to the above solution with stirring. After the addition,
the resulting mixture was heated to reflux for 6 h. The
mixture was filtered to remove the ammonium salt and the
filtrate was evaporated under reduced pressure to remove the
excess amine and chlorotrimethylsilane. The residue was
dissolved in CH Cl (10 mL) and washed with sat. NaHCO .
2
2
(
2 × 5 mL). The extracts were dried and filtered through a
short column of silica gel to remove the sodium salt. Upon
concentration, the desired carbonyl products were obtained
1
in pure form. For all products reported in Table 2, full H and
13
C NMR data were compared with those of the pure sample
2
2
3
2
5
obtained from commercial sources, or with reported data.
The organic extract was dried over MgSO and concentrated
4
(
14) Spectral Data for the Hydrolyzed Products:
1
to give the desired compound 20 (0.46 g, 100%). H NMR
1
8
1
,2-O-Isopropylidene-a-d-glucofuranose: mp 154–158
(
400 MHz, CDCl ): d = 3.64 (d, J = 12 Hz, 2 H), 3.55 (s, 2
3
1
°
C (dec.). H NMR (400 MHz, D O): d = 5.90 (d, J = 4 Hz, 1
2
H), 3.52 (d, J = 12 Hz, 2 H), 1.41 (s, 3 H), 1.37 (s, 3 H), 0.79
H), 4.58 (d, J = 4 Hz, 1 H), 4.20 (s, 1 H), 3.97 (d, J = 8 Hz,
H), 3.78 (m, 1 H), 3.68 (d, J = 12 Hz, 1 H), 3.97 (d, J = 8
13
(
(
(
s, 3 H), 0.09 (s, 9 H). C NMR (100 MHz, CDCl ): d = 97.5
3
1
C), 66.2 (CH ), 65.2 (CH ), 35.0 (C), 27.0 (CH ), 21.2
2
2
3
Hz, 1 H), 3.52 (dd, J = 6 Hz, 1 H), 1.39 (s, 3 H), 1.24 (s, 3
CH ), 18.3 (CH ), –0.1 (CH ). Anal. Calcd for C H O Si:
3
3
3
11 24
3
H). 13C NMR (100 MHz, D O): d = 112.5 (C), 104.6 (CH),
2
C, 56.85; H, 10.41. Found: C, 56.77; H, 10.21.
8
2
4
9
2
3
4.3 (CH), 79.6 (CH), 78.6 (CH), 68.2 (CH), 63.4 (CH2),
(17) Coppola, G. M. Synthesis 1984, 1021.
(18) Goud, P. M.; Venkatachalam, T. K.; Uckun, F. M. Synth.
Commun. 2003, 33, 1185.
19) Kobayashi, S.; Nagayama, S.; Busujima, T. J. Am. Chem.
Soc. 1998, 120, 8287.
5.4 (CH ), 25.0 (CH ).
3
3
2
1 1
-Propylbenzaldehyde: H NMR (400 MHz, CDCl ): d =
3
.98 (s, 1 H), 7.81 (d, J = 6.8 Hz, 2 H), 7.34 (d, J = 6.8 Hz,
H), 2.68 (t, J = 7 Hz, 2 H), 1.68 (m, 2 H), 0.96 (t, J = 7 Hz,
(
H). 13C NMR (100 MHz, CDCl ): d = 191.64 (CH), 150.1
3
Synlett 2007, No. 2, 283–287 © Thieme Stuttgart · New York