Two Asymmetric Approaches to Muscarine
FULL PAPER
ˆ
separated. The aqueous layer was extracted with dichloromethane
(40 mL), the combined organic solutions washed with brine
(40 mL), dried, and the solvents evaporated. Chromatography (10%
EtOAc in petroleum ether) of the residue gave the iodotetrahydrofu-
ran 39 (0.45 g, 68%) as a pale yellow oil. [α]2D0 ϭ ϩ18.2 (c ϭ 1.2,
and the EPSRC, Rhone-Poulenc-Rorer, and Cardiff University for
financial support.
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CH2Cl2). H NMR (400 MHz, CDCl3): δ ϭ 0.93 (s, 9 H), 1.34 (d,
J ϭ 6.6 Hz, 3 H, 5-CH3), 1.55 (app. br. s, 1 H, OH), 3.65 (dd, J ϭ
10.5, 5.8 Hz, 1 H, 1Ј-Ha), 3.69Ϫ3.73 (m, 1 H, 2-H), 3.70 (qd, J ϭ
6.6, 3.6 Hz, 5-H), 3.82 (dd, J ϭ 10.5, 4.3 Hz, 1 H, 1Ј-Hb), 4.19 (dd,
J ϭ 4.3, 3.6 Hz, 1 H, 3-H), 4.34 (app. br. t, J ca. 3.9 Hz, 1 H,
4-H), 7.27Ϫ7.38 (m, 6 H), 7.60Ϫ7.68 (m, 4 H) ppm. 13C NMR
(100.6 MHz, CDCl3): δ ϭ 19.7 (5-CH3), 20.5 (C), 27.3 (3 ϫ CH3),
36.0 (3-CH), 68.3 (1Ј-CH2), 77.8 (4-CH), 79.4 (5-CH), 82.1 (2-CH),
128.1 (4 ϫ CH), 130.2 (2 ϫ CH), 134.7 (2 ϫ C), 136.1 (4 ϫ CH)
ppm. IR (film): ν˜ ϭ 3425, 1471, 1428, 1261 cmϪ1. MS (APcI):
m/z ϭ 419 (Mϩ Ϫ Ph, 40%), 291 (Mϩ Ϫ Ph-HI, 100%). HRMS
(NH4CI): calcd. for C22H33INO3Si 514.1274 [M ϩ NH4ϩ], found
514.1271. C22H29IO3Si: calcd. C 53.23, H 5.89; found C 53.08, H
6.12.
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[10]
[11]
(2S,4R,5S)-2-O-(tert-Butyldiphenylsilylmethyl)-5-methyltetrahydro-
furan-4-ol (40a): The iodotetrahydrofuran 39 (0.45 g, 1.22 mmol),
triethylamine (0.34 mL, 2.44 mmol), and 10% palladium on carbon
(0.11 g) were stirred in ethyl acetate (10 mL) at ambient tempera-
ture under an atmosphere of hydrogen for 16 h. The resulting slurry
was filtered through Celite and the solid washed with ethyl acetate.
The combined filtrate and washings were diluted with diethyl ether
(20 mL), the solution washed with 1 hydrochloric acid (40 mL)
and brine (20 mL), dried, and the solvents evaporated to give the
tetrahydrofuran 40a (0.33 g, 91%) as a colourless oil. [α]2D0 ϭ ϩ4.3
(c ϭ 1.5, CH2Cl2). 1H NMR (400 MHz, CDCl3): δ ϭ 0.98 (s, 9 H),
1.15 (d, J ϭ 6.4 Hz, 3 H, 5-CH3), 1.81 (ddd, J ϭ 10.2, 6.7, 3.5 Hz,
1 H, 3-Ha), 2.04Ϫ2.12 (m, 1 H, 3-Hb), 3.59 (dd, J ϭ 10.8, 6.7 Hz,
1Ј-Ha), 3.64 (dd, J ϭ 10.8, 4.2 Hz, 1 H, 1Ј-Hb), 3.83 (qd, J ϭ 6.4,
3.6 Hz, 1 H, 5-H), 3.94 (app. br. td, J ϭ 6.7, 3.6 Hz, 1 H, 4-H),
4.15Ϫ4.21 (m, 1 H, 2-H), 7.29Ϫ7.37 (m, 6 H), 7.60Ϫ7.66 (m, 4 H)
ppm. 13C NMR (100.6 MHz, CDCl3): δ ϭ 18.0 (C), 18.2 (5-CH3),
25.8 (3 ϫ CH3), 35.4 (3-CH2), 65.0 (1Ј-CH2), 75.7 (4-CH), 76.5 (2-
CH), 81.3 (5-CH), 126.7 (4 ϫ CH), 128.6 (2 ϫ CH), 133.8 (2 ϫ
C), 134.6 (4 ϫ CH) ppm. IR (film): ν˜ ϭ 3397, 1472, 1428, 1390,
1260, 1111 cmϪ1. MS (APcI): 293 (Mϩ Ϫ Ph, 100%). HRMS
(NH4CI): calcd. for C22H34NO3Si 388.2308 (M ϩ NH4ϩ), found
388.2312.
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
(2S,4R,5S)-(4-Hydroxy-5-methyltetrahydrofuran-2-yl)methanol
(40b): Ammonium fluoride (0.27 g, 7.17 mmol) was added to a
solution of the tetrahydrofuran 40a (0.29 g, 1.19 mmol) in meth-
anol (5 mL), the resulting solution stirred at ambient temperature
for 16 h, and then evaporated. The resulting brown solid was sepa-
rated by column chromatography (10% MeOH in CH2Cl2) to give
the diol 40b (0.09 g, 56%) as a colourless oil. [α]2D0 ϭ Ϫ5.8 (c ϭ 0.2,
CHCl3), (ref.[19] [α]2D0 ϭ Ϫ6.0 (c ϭ 0.5, CHCl3). 1H NMR
(400 MHz, CDCl3): δ ϭ 1.17 (d, J ϭ 6.4 Hz, 3 H, 5-CH3), 1.54 (br.
s, 2 H, 2 ϫ OH), 1.76 (ddd, J ϭ 13.2, 6.5, 3.5 Hz, 1 H, 3-Ha), 1.96
(ddd, J ϭ 13.2, 9.1, 6.4 Hz, 3-Hb), 3.43 (dd, J ϭ 11.9, 4.9 Hz, 1 H,
1Ј-Ha), 3.70 (dd, J ϭ 11.9, 3.0 Hz, 1 H, 1Ј-Hb), 3.85 (qd, J ϭ 6.4,
3.5 Hz, 1 H, 5-H), 3.93 (m, 1 H, 4-H), 4.17Ϫ4.21 (m, 1 H, 2-H)
ppm. 13C NMR (100.6 MHz, CDCl3): δ ϭ 18.9 (5-CH3), 35.1 (3-
CH2), 63.7 (1Ј-CH2), 76.6 (4-CH), 77.7 (2-CH), 81.8 (5-CH) ppm.
HRMS: calcd. for C6H13O3 [Mϩ ϩ H] 133.0865, found 133.0864.
These data correspond to those previously reported.[19]
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Acknowledgments
We thank the EPSRC Mass Spectrometry Service, University Col-
lege, Swansea for recording high resolution mass spectrometric data
Eur. J. Org. Chem. 2004, 1973Ϫ1982
2004 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1981