A. Temperini et al. / Tetrahedron Letters 52 (2011) 3179–3182
3181
(CF3SO3Cu)2 . C6H5CH3
THF, RT
(Me)3Si
RO
(Me)3Si
PhSe
PhSeSePh
ROH +
O
O
1
2c
5
Scheme 2. Reaction of alcohols 1 with SEM-phenyl selenide 2c.
5. (a) Bonner, W. A.; Robinson, A. J. Am. Chem. Soc. 1950, 72, 354–356; (b) Tingoli,
M.; Temperini, A.; Testaferri, L.; Tiecco, M.; Resnati, G. Carbohydr. Lett. 1998, 3,
39–46.
6. (a) Zuurmond, H. R.; van der Klein, P. A. M.; van der Meer, P. H.; van der Marel,
G. A.; van Boom, J. H. Recl. Trav. Chim. Pays-Bas 1992, 111, 365–366; (b) Mehta,
S.; Pinto, M. J. Org. Chem. 1993, 58, 3269; (c) Tingoli, M.; Tiecco, M.; Testaferri,
L.; Temperini, A. J. Chem. Soc., Chem. Commun. 1994, 1883–1884.
7. Temperini, A.; Terlizzi, R.; Testaferri, L.; Tiecco, M. Synlett 2009, 2429–2432.
8. (a) Wuts, P. G. M.; Green, T. W. Protective Groups in Organic Chemistry, 4th ed.;
John Wiley & Sons: New York, 2007; (b) Kocienski, P. J. Protecting Groups, 3rd
ed.; George Thieme Verlag: Stuttgart, 2004.
9. (a) Corey, E. J. Tetrahedron Lett. 1976, 17, 809–812; (b) Stork, G.; Takahashi, T. J.
Am. Chem. Soc. 1977, 99, 1275–1276; (c) Lipshutz, B. H.; Pegram, J. J.
Tetrahedron Lett. 1980, 21, 3343–3346; (d) Wada, T.; Tobe, M.; Nagayama, T.;
Furusawa, K.; Sekine, M. Tetrahedron Lett. 1995, 36, 1683–1684.
Table 3
2-(Trimethylsylil)ethoxymethylation of alcohols
promoted by copper(I) triflate toluene complex
1 with SEM-phenyl selenide 2c
Entry
Product 5a R1 = CH2OCH2CH2Si(Me)3
Time (h)
1
Yieldb (%)
76
OR1
CF3
1
5b
5e
OR1
2
3
1.5
3
60c,d
HO
OR1
10. (a) Stern, R.; English, J.; Cassidy, H. G. J. Am. Chem. Soc. 1957, 79, 5793–5997; (b)
Kluge, A. F.; Untch, K. G.; Fried, J. H. J. Am. Chem. Soc. 1972, 94, 7827–7832; (c)
Auerbach, J.; Weinreb, S. M. J. Chem. Soc., Chem. Commun. 1974, 298–299.
11. Marcune, B. F.; Karady, S.; Dolling, U-H.; Novak, T. J. J. Org. Chem. 1999, 64,
2446–2449.
O
60e
BnO
BnO
5f
BnO
OMe
12. (a) Anciaux, A.; Eman, A.; Dumont, W.; Van Ende, D.; Krief, A. Tetrahedron Lett.
1975, 16, 1613–1616; (b) Seebach, D.; Meyer, N.; Beck, A. K. Liebigs Ann. Chem.
1977, 846–858; (c) Reich, H. J.; Chow, F.; Shah, S. K. J. Am. Chem. Soc. 1979, 101,
6638–6648; (d) Nishiyama, Y.; Nakata, S.; Hamanaka, S. Chem. Lett. 1991,
1775–1776.
13. General procedure for the protection of alcohols 1 as MOM-derivatives. To a
mixture of alcohol 1 (1 mmol), the O, Se acetal 2a (1.4 mmol), solid potassium
carbonate (2.0 mmol) and activated 3 Å molecular sieves (0.20 g) in dry ethyl
acetate (16 mL), solid N-iodosuccinimide (1.4 mmol) was added in portion at
room temperature. The mixture was stirred under inert atmosphere and
monitored by TLC. Reaction times ranged from 0.5 to 2 h. The brown colored
reaction mixture was quenched into 20 mL of 10% aqueous sodium thiosulfate
pentahydrate solution, mixed, and separated. The aqueous phase was extracted
with 10 mL of ethyl acetate and the combined organic phases were washed
with 10 mL of brine, dried over sodium sulfate and concentrated. Purification
by silica gel column chromatography afforded the MOM-ether derivative 3.
O
4
5
5m
5n
2
56
64
O
OR1
2
2
OR1
12
O
BocNH
OR1
OR1
6
7
5p
5q
1.5
7
52e
64
3
PhthN
3
All the products were characterized by 1H and 13C NMR and mass spectroscopy.
Yields of isolated products; P 97% pure material by 1H NMR.
1.0 equiv of copper(I) triflate was employed.
a
b
c
d
The filtrate poured into 20 mL of 4 N aqueous NH4Cl solution. A 8% of the
Physical and spectral data of
a selected compound is reported. 2-{1-
starting alcohol was recovered.
e
[(Methoxymethoxy)methyl]propyl}-1H-isoindole-1,3(2H)-dione (3a): Yield
74%; oil; 1H NMR (200 MHz, CDCl3): d = 7.88–7.76 (m, 2H), 7.74–7.65 (m,
2H), 4.56 (AB system, 2H), 4.48–4.30 (m, 1H), 4.09 (t, 1H, J = 10.1 Hz), 3.80 (dd,
A 10% of the starting alcohol was also recovered.
1H, J = 10.1, 5.1 Hz), 3.24 (s, 3H), 2.15–1.65 (m, 2H), 0.91 (t, 3H, J = 7.4 Hz). 13
C
NMR (50 MHz, CDCl3): d = 166.1 (2C), 133.8 (2C), 131.8 (2C), 123.1 (2C), 96.2,
67.0, 55.2, 53.0, 22.0, 10.7.
14. Yoshimatsu, M.; Fujimoto, M.; Shimizu, H.; Hori, M.; Kataoka, T. Chem. Pharm.
Bull. 1993, 41, 1160–1162.
In conclusion a new and simple procedure for the activation of
MOM-, MEM-, and SEM-phenyl selenides 2a–c with iodonium or
copper(I) ions and the subsequent reaction with alcohols to give
the corresponding alkoxymethyl ethers was described. It is also
remarkable that these reactions occur under neutral conditions.
The results here presented, therefore, favorably compare with
other methods described in the literature.
15. General procedure for the protection of alcohols
1 as MEM-derivatives. The
procedure adopted for the synthesis of MOM-derivatives 3 was employed for
the synthesis of MEM-derivatives 4 with the sole exception that O, Se acetal 2b
was used. Physical and spectral data of a selected compound are reported.
Methyl 2,3,4-tri-O-benzyl-6-O-[(2-methoxyethoxy)methyl]-a-D-glucopyrano-
side (4f): Yield 73%; oil; 1H NMR (200 MHz, CDCl3): d = 7.45–7.20 (m, 15H),
5.05–4.55 (m, 9H), 4.01 (t, 1H, J = 9.1 Hz), 3.85–3.46 (m, 9H), 3.39 (s, 3H), 3.35
(s, 3H). 13C NMR (50 MHz, CDCl3): d = 138.7, 138.2, 138.0, 128.4 (8C), 128.1
(2C), 127.9 (2C), 127.7 (2C), 127.5, 98.1, 95.9, 82.0, 79.7, 77.6, 75.6, 74.9, 73.3,
71.6, 69.7, 66.9, 66.4, 58.9, 55.1.
Acknowledgments
16. General procedure for the synthesis of the O, Se acetals 2a–c. All the O, Se acetals
2a–c were prepared from the corresponding alkyl chloromethyl ethers by a
slight modification of the original procedure for the preparation of sodium
phenylselenolate.18 In a 100 mL three-necked flask equipped with a reflux
condenser were placed diphenyl diselenide (1.26 g, 4 mmol) and 32 mL of dry
DMF. The solution was heated at 60 °C and stirred rapidly under nitrogen while
NaBH4 (0.30 g, 8 mmol) was added in portion. Hydrogen was evolved and the
reaction mixture turned colorless and homogeneous upon complete reduction
of the selenide. The reaction was heated at 110 °C for 1 h and then cooled to
35 °C. Net 2-(trimethylsilyl)ethoxymethyl chloride (2.5 mL, 12 mmol) was
added dropwise to the orange solution. (All equipment that came in contact
with the alkyl chloromethyl ether was immediately immersed in a 4 N NH4OH
bath). After stirring at 35 °C for 5 h, 4 N aqueous NH4OH (5 mL) was added
carefully to the white suspension. The entire product mixture was poured into
50 mL of water and 40 mL of diethyl ether, mixed, and separated. The aqueous
phase was extracted with 20 mL of diethyl ether and the combined organic
phases were washed with H2O (4 Â 10 mL), 10 mL of brine, dried over sodium
sulfate, and concentrated. Purification by silica gel column using a mixture of
Et2O-light petroleum (2:98) as eluant gave the SEM-ether derivative 2c (1.9 g,
82%) as a light yellow oil. Trimethyl{2-[(phenylseleno)methoxy]ethyl}silane
(2c). 1H NMR (200 MHz, CDCl3): d = 7.68–7.52 (m, 2H), 7.31–7.22 (m, 3H), 5.28
(s, 2H), 3.71–3.60 (m, 2H), 1.00–0.89 (m, 2H), 0.01 (s, 9H). 13C NMR (50 MHz,
Financial support from MIUR, National Projects PRIN 2007, Con-
sorzio CINMPIS, Bari and University of Perugia is gratefully
acknowledged.
References and notes
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