1
3
13
13
LETTER
Synthesis of 1,2- C -L-Fucose, 1,2- C -Fucono-g-lactone and 1,2- C -Fucono-g-lactol
2687
2
2
2
(
6) (a) Wendeborn, S.; Nussbaumer, S.; Hannes, R. F.; Joerg,
M.; Pachlatko, J. P. Tetrahedron Lett. 2002, 43, 31. (b) Xu,
Z.; Johannes, C. W.; Salman, S. S.; Hoveyda, A. H. J. Am.
Chem. Soc. 1996, 118, 10926.
structures where the 1,2-trans isomer shows the more
1
3
12
downfield C shift for C1 and the smaller J . The
1
,2
nomenclature is consistent with IUPAC conventions for C6
1
3
furanosides. This reaction has also been carried out on
multi-gram scale.
(
7) Typical Experimental for Synthesis of 5.
To a solution of 4 (2.169 g, 8.66 mmol) in MeOH (146.5
(12) (a) Takahasi, S.; Kuzuhara, H. J. Chem. Soc., Perkin Trans.
1 1997, 607. (b) Kinoshita, T.; Miwa, T.; Clardy, J.
Carbohydr. Res. 1985, 143, 249. (c) Angyal, S. J.; Pickles,
V. A. Aust. J. Chem. 1972, 25, 1695.
mL) and H O (19 mL) was added p-TSA (165 mg, 0.866
2
mmol) and the reaction mixture was stirred at 60 °C until no
starting material was visible by TLC. The solvent were
removed and chromatography afforded 5 as a white solid
(13) McNaught, A. D. Pure Appl. Chem. 1996, 68, 1919.
(14) The unlabelled peracylated analogue of 7 has been
described, prepared by homologation from the precursor C5
aldehyde: Shunya Takahashi, S.; Kuzuhara, H. J. Chem.
Soc., Perkin Trans. 1 1997, 607.
(15) The crystal structures both showed four independent
molecules in the unit cell, each differing in conformations
about C–O bonds, with little evidence of intramolecular H-
1
(
1.172 g, 7.10 mmol, 82%). H NMR (300 MHz, MeOD):
1
3
13
d = 4.34 [1 H, ddd, J = 142.8, 8.7, 4.9 Hz, CO CH(OH)],
4
1
3
13
.22–4.15 [1 H, m, CO CH(OH)CH(OH)], 3.95–3.87 [1
H, m, CH(OH)CH(OH)CH ], 3.95–3.87 (1 H, m, CHCH ),
3
3
1
3
1
.32 (3 H, d, J = 6.4 Hz, OCHCH3). C NMR (75.5 MHz,
1
3
13
MeOD): d = 177.5, 176.8 [d, J = 55.9 Hz, CO CH(OH)],
1
3
13
7
7.2, 76.4 (d, J = 55.9 Hz, CO CH(OH)]. HRMS (+ES):
1
3
m/z calcd for C C H O : 182.0939. Found: 182.0936 [M +
bonding. These structures are also noteworthy as there are
4
2
10
5
+
22
13
NH ] . Mp 91–95 °C. [a] +60.8 (c 0.5, H O).
few X-ray structures of C -labelled compounds.
4
D
2
2
(
(
8) Matsumoto, T.; Hosoya, T.; Suzuki, K. J. Am. Chem. Soc.
992, 114, 3568.
9) Balitz, D. M.; O’Herron, F. A.; Bush, J.; Vyas, D. M.;
Netiletron, D. E.; Grulich, R. E.; Bradner, W. T.; Doyle, T.
W.; Arnold, E.; Clardy, J. J. Antibiot. 1981, 34, 1544.
(16) Typical Experimental for Synthesis of 8.
1
To a solution of 7 (150 mg, 0.295 mmol) in dioxane–H O
was added concd HCl. The mixture was stirred overnight.
Filtration through Amberlite and removal of the solvents
2
afforded the crude sugar. Then, Ac O (10 equiv, 2.95 mmol,
2
(
(
10) Jain, T. C.; Simolike, G. C.; Jackman, L. M. Tetrahedron
Lett. 1983, 39, 599.
0.278 mL), pyridine (12 equiv, 3.54 mmol, 0.286 mL) and
CH Cl (5 mL) were added and the mixture stirred for 14 h.
2
2
11) Typical Experimental for Synthesis of 7:
DIBAL (0.52 mL, 0.52 mmol) was added dropwise to a
solution of 6 (86.6 mg, 0.17 mmol) in CH Cl (3 mL) at
The reaction was quenched by the addition of H O and
2
washed with CuSO solution. Purification by
4
chromatography yielded 8 as white crystals (94.7 mg, 0.28
2
2
1
–78 °C. After 1 h the reaction was quenched with MeOH and
mmol, 96%). H NMR (400 MHz, CDCl ): b-anomer, d =
3
the solvent was removed. The colourless oil was purified by
5.68 (1 H, dd, J = 174.5, 7.9 Hz, H1), 5.60 (1 H, dd,
J = 113.4, 10.2, 7.9 Hz), 5.33–5.27 (1 H, m), 5.13–5.08 (1 H,
m), 3.99–3.94 (1 H, dd, J = 12.1, 6.4, 6.0 Hz), 2.20, 2.13,
2.05, 2.01 (3 H, s), 1.24 (3 H, d, J = 6.4 Hz, H6); a-anomer,
d = 6.65 (1 H, dd, J = 177.8, 3.4 Hz, H1), 5.35 (2 H, m), 5.08
(1 H, ddd, J = 153.7, 9.8, 3.4 Hz, H2), 4.28 (1 H, dd,
J = 12.8, 6.5 Hz), 1.12 (3 H, d, J = 6.4 Hz, H6). 3C NMR
chromatography to give 7 as white crystals (84 mg, 0.17
1
mmol, 97%). H NMR (300 MHz, CDCl ): b-anomer, d =
3
1
13
3 13
5
.16 (1 H, ddt, J
= 171.8 Hz, J
= 12.1 Hz and
CH
CHOH
3
13 13
J
= 4.1 Hz), 4.11–4.07 (1 H, m), 4.00–3.80 (2 H, m),
CH CH
3.82 (1 H, ddd, J = 12.1, 4.9, 1.5 Hz), 3.68–3.63 (1 H, m),
1
1
J
.21 (3 H, d, J = 6.4 Hz); a-anomer, d = 5.06 (1 H, dd,
1
13
3 13
= 174.8 Hz, J
= 12.1 Hz), 4.00–3.82 (4 H, m),
(75.5 MHz, CDCl ): b-anomer, d = 92.6 (d, J = 47.4 Hz),
CH
CHOH
3
3
.56 (1 H, ddd, J = 12.1, 4.9, 2.3 Hz), 1.12 (3 H, d, J = 6.0
68.3 (d, J = 47.4 Hz). a-anomer, d = 90.50 (d, J = 48.3 Hz),
66.85 (d, J = 48.3 Hz). HRMS (EI): m/z calcd for
1
3
Hz). Both anomers, d = 0.92–0.88 (54 H, m). C NMR (75.5
MHz, CDCl ): b-anomer, d = 97.9 (d, J
1
13 13
13
+
= 41.4 Hz),
C12 C H O : 357.1069. Found: 357.1067 [M + Na] . a-
3
CH CH
2 20 9
1
13 13
22
22
8
J
0.8 (d, J
= 41.4 Hz). a-anomer, d = 104.0 (d,
Anomer: [a]D – 48 (c 1, CHCl ); b-anomer: [a] –113 (c
3 D
CH CH
1
13 13
CH CH
1 13 13
= 44.3 Hz), 81.8 (d, J
= 44.3 Hz). HRMS
1, CHCl3).
CH CH
1
2
3
(
+ES): m/z calcd for C C H O Si : 531.33245. Found:
(17) (a) Kinoshita, T.; Miwa, T.; Clardy, J. Carbohydr. Res.
1985, 143, 249. (b) Allavudeen, S. S.; Kuberan, B.;
Loganathan, D. Carbohydr. Res. 2002, 337, 965.
2
2
54
5
3
+
531.3243 [M + Na] . These assignments are consistent with
data for a number of related furanose and furanoside
Synlett 2005, No. 17, 2685–2687 © Thieme Stuttgart · New York