1
922
N. Sumida et al.
LETTER
(7) (a) H PO : Davey, W.; Gwilt, J. R. J. Chem. Soc. 1957,
Table LiBF Catalyzed Acylal Formation
4
3
4
1
008. (b) H SO : Tomita, M.; Kikuchi, T.; Bessho, K.; Hori,
2 4
2
Entry Substrate
(R CO) O
(
Condition
(°C/h)
Yield
(%)a
2
T.; Inubushi, Y. Chem. Pharm. Bull. 1963, 11, 1484.
c) See also: Freeman, F.; Karchefski, E. M. J. Chem. Eng.
equiv)
(
Data 1977, 22, 355. (d) HClO : Marshall, J. A.; Wuts, P. G.
M. J. Org. Chem. 1977, 42, 1794.
8) For recent leading references see: (a) LiBr: Kumar, H. M.
S.; Reddy, B. V. S.; Reddy, P. T.; Yadav, J. S. J. Chem. Res.,
Synop. 2000, 86. (b) TMSCl/NaI: Deka, N.; Borah, R.;
Kalita, D. J.; Sarma, J. C. J. Chem. Res., Synop. 1998, 94.
4
1
2
3
4
5
6
7
8
9c
0
PhCHO
2a (2)
2b (2)
2c (2)
2d (2)
2a (2)
2a (2)
2a (4)
2a (2)
2a (2)
2a (2)
40/22
40/25
40/24
60/25
40/24
40/19
60/25
40/22
60/23
40/21
95
93
85
91
92
95
93b
85
90
91
(
PhCHO
PhCHO
PhCHO
(
c) Sc(OTf) : Aggarwal, V. K.; Fonquerna, S.; Vennall, G. P.
3
Synlett 1998, 849. (d) FeSO : Jin, T.-S.; Du, G.-Y.; Li, T.-S.
4
p-MeC H CHO
6
4
Indian J. Chem. 1998, 37B, 939. (e) FeCl : Trost, B. M.;
3
Lee, C. B.; Weiss, J. M. J. Am. Chem. Soc. 1995, 117, 7247.
p-MeOC H CHO
6
4
(
f) See also: Trost, B. M.; Lee, C. B. J. Am. Chem. Soc. 2001,
p-HOC H CHO
123, 3671. (g) Cu(OTf) : Chandra, K. L.; Saravanan, P.;
2
6
4
Singh, V. K. Synlett 2000, 359. (h) NBS: Karimi, B.;
Seradj, H.; Ebrahimian, G. R. Synlett 2000, 623. (i) I2:
Deka, N.; Kalita, D. J.; Borah, R.; Sarma, J. C. J. Org. Chem.
p-ClC H CHO
6
4
p-NO C H CHO
2
6
4
1
997, 62, 1563.
R
(
9) For recent leading references see: (a) Envirocat EPZR :
Bandgar, B. P.; Mahajan, N. P.; Mulay, D. P.; Thote, J. L.;
Wadgaonkar, P. P. J. Chem. Res., Synop. 1995, 470.
1
CHO
(
b) Expansive graphite: Jin, T.-S.; Du, G.-Y.; Zhang, Z.-H.;
3
+
Li, T.-S. Synth. Commun. 1997, 27, 2261. (c) Fe -
montmorillonite: Li, T.-S.; Zhang, Z.-H.; Gao, Y.-J. Synth.
Commun. 1998, 28, 4665. (d) HZSM-5: Joshi, M. V.;
Narasimhan, C. S.; Mukesh, D. Zeolites 1995, 15, 597.
1
1
2a (2)
25/22
89
O
CHO
CHO
1
1
1
1
1
1
2
3
4
5
6
7
2a (2)
2a (5)
2a (5)
2a (2)
2a (2)
2a (2)
40/16
40/21
40/24
75/22
40/24
40/24
86d
70
Ph
(
e) Montmorillonite K-10: Zhang, Z.-H.; Li, T.-S.; Fu, C.-G.
n-C H CHO
5
11
J. Chem. Res., Synop. 1997, 174. (f) See also: Karmakar,
D.; Prajapati, D.; Sandhu, J. S. J. Chem. Res., Synop. 1998,
c-C H CHO
71
6
11
3
82. (g) PVC-FeCl : Li, Y.-Q. Synth. Commun. 2000, 30,
3
3
913. (h) Sulfated zirconia: Raju, S. V. N. J. Chem. Res.,
t-C H CHO
75
4
9
2
–
Synop. 1996, 68. (i) TiO /SO : Jin, T.-S.; Ma, Y.-R.; Sun,
2
4
n-C H (CH )C=O
n.r.e
n.r.e
X.; Liang, D.; Li, T.-S. J. Chem. Res., Synop. 2000, 96.
j) Zeolite Y: Ballini, R.; Bordoni, M.; Bosica, G.; Maggi,
4
9
3
(
Ph(CH )C=O
3
R.; Sartori, G. Tetrahedron Lett. 1998, 39, 7587. (k) -
Zeolite: Kumar, P.; Hegde, V. R.; Kumar, T. P. Tetrahedron
Lett. 1995, 36, 601. (l) Y-Zeolite: Pereira, C.; Gigante, B.;
Marcelo-Curto, M. J.; Carreyre, H.; Pérot, G.; Guisnet, M.
Synthesis 1995, 1077.
a
b
c
d
e
Isolated yields.
Yield refers to pure triacetate.
LiBF (30 mol%) was used.
4
E/Z = 100/0.
No reaction.
(10) For reviews see: (a) Coleman, P. J. In Encyclopedia of
Reagents for Organic Synthesis, Vol. 5; Paquette, L. A., Ed.;
Wiley: Chichester, 1995, 3164. (b) Coleman, P. J. In
Handbook of Reagents for Organic Synthesis Acidic and
Basic Reagents; Reich, H. J.; Rigby, J. H., Eds.; Wiley:
Chichester, 1999, 231. (c) Babu, B. S.; Balasubramanian, K.
K. Acros Org. Acta 2000, 7, 1.
References
(
(
(
1) Kochhar, K. S.; Bal, B. S.; Deshpande, R. P.; Rajadhyaksha,
S. N.; Pinnick, H. W. J. Org. Chem. 1983, 48, 1765.
2) Greene, T. W.; Wuts, P. G. M. Protective Groups in Organic
Synthesis, 3rd ed.; Wiley: New York, 1999, 306.
3) (a) Saucy, G.; Marbet, R.; Lindlar, H.; Isler, O. Helv. Chim.
Acta 1959, 42, 1945. (b) Blanc, P.-Y. Helv. Chim. Acta
(11) The following procedure is representative (Table, entry 1). A
mixture of benzaldehyde (212 mg, 2 mmol), Ac O (408 mg,
2
4 mmol), and LiBF (0.2 mmol) was stirred at 40 °C for 22
4
h (monitored by TLC). After the reaction was quenched with
3
1
1
961, 44, 1. (c) Snider, B. B.; Amin, S. G. Synth. Commun.
978, 8, 117. (d) McDonald, E.; Suksamrarn, A.; Wylie, R.
H O (20 cm ), the resulting mixture was extracted with
2
3
EtOAc (2 30 cm ). The organic layer was successively
3
D. J. Chem. Soc., Perkin Trans 1 1979, 1893. (e) Banks, R.
E.; Miller, J. A.; Nunn, M. J.; Stanley, P.; Weakley, T. J. R.;
Ullah, Z. J. Chem. Soc., Perkin Trans 1 1981, 1096.
washed with sat. NaHCO solution (2 20 cm ) and with
3
3
brine (20 cm ), and dried (Na SO ). Evaporation and
2
4
purification over silica gel by column chromatography
(5% EtOAc–hexane) provided acetoxyphenylmethyl acetate
(396 mg, 95%).
(
4) (a) Whitesides, G. M.; Filippo, J. S. Jr. J. Am. Chem. Soc.
1970, 92, 6611. (b) Held, H.; Rengstl, A.; Mayer, D. In
Ullmann’s Encyclopedia of Industrial Chemistry, 5th ed.,
Vol. A1; Gerhartz, W., Ed.; VCH: New York, 1985, 68.
5) Frick, J. G. Jr.; Harper, R. J. Jr. J. Appl. Polym. Sci. 1984, 29,
(12) The reaction of pentanal (1 mmol) and benzaldehyde
(1 mmol) with Ac O (2 mmol) using LiBF (0.1 mmol) at
2
4
(
(
40 °C for 22 h afforded acetoxypentyl acetate and acetoxy-
phenylmethyl acetate in 33% and 74% yields, respectively.
1
433.
6) For a review see: Sydnes, L. K.; Sandberg, M. Tetrahedron
997, 53, 12679.
1
Synlett 2001, No. 12, 1921–1922 ISSN 0936-5214 © Thieme Stuttgart · New York