2452
L. M. H. Leung et al. / Tetrahedron: Asymmetry 16 (2005) 2449–2453
concentration in vacuo delivered crude 1, which was
purified by column chromatography (EtOAc/petroleum
ether 2:8) to afford a clear oil (128 mg, 85%).
J = 5.0 Hz), 3.14 (1H, td, J = 4.0, 2.5 Hz), 3.09 (1H,
ddd, J = 4.5, 4.0, 2.5 Hz), 2.75–2.85 (4H, m), 2.62 (1H,
d, J = 5.0 Hz); 13C NMR (75 MHz, CDCl3) 70.2, 52.6,
52.1, 44.6, 44.1.
4.2.2. From arabitol. Triisopropylbenzensulfonyl chlo-
ride (41.4 g, 0.137 mol) was added to a solution of L-
arabitol (10.0 g, 66.0 mmol) and DMAP (0.840 g,
6.88 mmol) in pyridine (150 mL) at 0 ꢁC. The reaction
mixture was stirred at 0 ꢁC for 24 h. HCl (2M,
920 mL) and Et2O (600 mL) were then added. The
aqueous layer was extracted with Et2O (2 · 500 mL),
washed with 2 M HCl (100 mL), 5% NaHCO3 (1 L)
and brine (400 mL). Filtration and concentration in
vacuo led to a white solid, which was dissolved in
Et2O/DMF (1:1, 2190 mL) and cooled to 0 ꢁC. NaH
(60% dispersion in mineral oil, 9.47 g, 0.237 mol) was
added and the mixture was stirred at 0 ꢁC for 1 h. BnBr
(11.8 mL, 99.2 mmol) was added and the reaction mix-
ture warmed to room temperature. NaI (14.7 g,
98.7 mmol) was added and the mixture stirred for
24 h. Satd NH4Cl (300 mL) and H2O (1.2 L) were then
added. The aqueous layer was extracted with Et2O
(2 · 300 mL), washed with brine (500 mL) and dried
over Na2SO4. Filtration, concentration in vacuo and
purification by flash column chromatography (EtOAc/
petroleum ether 2:8) delivered 1 as a clear oil (8.56 g,
63%). Bis-epoxide 1 can be further purified by distilla-
tion under reduced pressure (116 ꢁC, 0.6 mbar).
Acknowledgements
The authors would like to thank the EPSRC and CMS
Chemicals for financial support. We also wish to
acknowledge the use of the EPSRCÕs Chemical Data-
base service at Daresbury.15 We are grateful to Mr.
A. J. Boydell for obtaining spectroscopic data for 1.
References
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22
D
1
4.2.3. Data for ent-1. ½aꢀ ¼ þ29.8 (c 1.0, CHCl3); H
NMR (400 MHz, CDCl3) 7.25–7.37 (5H, m), 4.76 (1H,
d, J = 12.0 Hz), 4.65 (1H, d, J = 12.0 Hz), 3.17 (1H,
ddd, J = 6.0, 4.5, 3.0 Hz), 2.99 (1H, ddd, J = 5.5, 4.0,
2.5 Hz), 3.07 (1H, ddd, J = 5.5, 3.5, 2.5 Hz), 2.99 (1H,
dd, J = 6.5, 5.5 Hz), 2.79–2.84 (2H, m), 2.64–2.68 (2H,
m); 13C NMR (100 MHz, CDCl3) 137.9, 128.3 · 2,
127.7 · 3, 79.7, 72.2, 52.6, 50.9, 45.2, 43.1; IR (cmꢁ1):
3062 m, 3031 m, 2998 s, 2927 m, 2873 m, 1602 w,
1496 m and 1455 s; LRMS (CI) 224 (M þ NHþ4 , 60),
91 (100); HRMS (ES+) for C12H14O3Na (M+Na)+:
calcd 229.08406. Found 229.08315.
4.3. Preparation of (2S,4S)-1,2:4,5-Dianhydroarabitol 6
Triisopropylbenzensulfonyl chloride (4.29 g, 14.1 mmol)
was added to a solution of L-arabitol (1.05 g, 6.90 mmol)
and DMAP (83.0 mg, 0.68 mmol) in pyridine (15 mL) at
0 ꢁC. The reaction mixture was stirred at 0 ꢁC for 24 h.
HCl (2M, 92 mL) and Et2O (50 mL) were then added.
The aqueous layer was extracted with Et2O
(2 · 50 mL), washed with 2 M HCl (30 mL), 5% NaH-
CO3 (10 mL) and brine (50 mL). Filtration and concen-
tration in vacuo led to a white solid, which was dissolved
in THF (219 mL) and cooled to 0 ꢁC. NaH (60% disper-
sion in mineral oil, 0.92 g, 23.0 mmol) was added and
the mixture was stirred at 0 ꢁC for 1 h. Satd NH4Cl
(3 mL) was added and the slurry filtered through a col-
umn of Na2SO4. Concentration in vacuo and purifica-
tion by column chromatography (EtOAc/toluene 3:7)
afforded a colourless liquid (0.509 g, 63%).
7. Altenbach, H. J.; Merhof, G. F. Tetrahedron: Asymmetry
1996, 7, 3087–3090.
8. (a) Concellon, J. M.; Riego, E.; Rodriguez-Solla, H.;
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1H NMR data corresponded to previously reported val-
ues.4b: 1H NMR (300 MHz, CDCl3) 3.52 (1H, q,