950
C. Miculka
LETTER
(4) Bolli, M.; Micura, R.; Eschenmoser, A. Chem. Biol. 1997, 4,
309.
(5) Decker, P.; Schweer, H. Origins Life 1984, 14, 335.
(6) Harsch, G.; Bauer, H.; Voelter, W. Liebigs Ann. Chem. 1984,
623.
J = 3.8, 8.9, H-C(4)); 4.04 (dd, J = 4.6, 9.0, H-C(3)); 4.66 (dd,
J = 4, H-C(2)); 5.01 (d, J = 3.8, H-C(5)); 5.80 (d, J = 3.5, H-
C(1)).
Ribo-pentodialdose 4: 40 ml ion-exchange resin Amberlite IR-
120 (H+form) was added to a solution of 5.0 g (26.2 mmol) 3
in 50 ml of H2O and stirred at 45 °C for 2.5 h. The reaction
mixture was filtered and evaporated:3.83 g (98%) 4 as mixture
of isomers. Colorless foam. TLC (silica gel, CHCl3/MeOH/
H2O 85:30:2): Rf 0.28. 1H NMRand 13C NMRsee Table 1. IR
(KBr):3401s (br.), 2973m, 1656m, 1465s, 1420m, 1347m,
1264m, 1054s (br.), 566m (br.). FAB-MS:167 (2, MH2O+),
(7) Ranganayaki, S.; Srivastava, B.; Bahadur, K. Zbl. Bakt. II.
Abt. 1980, 135, 265.
(8) Hough, L.; Jones, J. K. N. J. Chem. Soc. 1951, 3191.
(9) Müller, D.; Pitsch, S.; Kittaka, A.; Wagner, E.; Wintner, C. E.;
Eschenmoser, A. Helv. Chim. Acta 1990, 73, 1410.
(10) van Ekenstein, W. A.; Blanksma, J. J. Chem. Zentralbl. 1914,
85, 965.
149 (13, MH+), 31 (100). Elem. anal.: calc: C5H8O5 0.6 H2O:
.
(11) Pitsch, S. Helv. Chim. Acta 1997, 80, 2286.
(13) Von Sonntag, C.; Dizdaroglu, M. Carbohydr. Res. 1977, 58,
21.
(13) (a) Steenken, S.; Goldbergerova, L. J. Am. Chem. Soc. 1998,
120, 3928. (b) Stelter, L.; Von Sonntag, C.; Schulte-Frohlinde,
D. Z. Naturforsch., B: Anorg. Chem., Org. Chem. 1975, 30B,
609.
(14) Kiang, A. K.; Loke, K. H. J. Chem. Soc. 1956, 480.
(15) Czernecki, S.; Ezzitouni, A.; Krausz, P. Synth. Commun.
1986, 11.
C 37.79, H, 5.84; found: C 38.01, H 6.15.
DL-Ribose 5: 95 mg (2.51 mmol; 0.28 eq.) NaBH4 in 5 ml H2O
was added to 1.33 g (8.98 mmol) 4 in 30 ml H2O. After 30 min
at r. t. 15 ml ion-exchange resin Amberlite IR-120 (H+form)
was added. The reaction mixture was stirred for 10 min and
filtered. 10 ml ion-exchange resin Amberlite IRA-400 (OH-
form) was added to the filtrate, stirred for 10 min, filtered and
evaporated: 0.86 g (64%) 5. Colorless foam. TLC (silica gel,
CHCl3/MeOH/H2O 85:30:2): Rf 0.17 (identical to natural D-
ribose).
(16) Paulsen, H.; Günther, Ch. Chem. Ber. 1977, 110, 2150.
(17) (a) Youssefyeh, R. D.; Verheyden, J. P. H.; Moffatt, J. G. J.
Org. Chem. 1979, 44, 1301. (b) Aparicio, F. J. L.; Benitez, F.
Z.; Gonzales, F. S. Carbohydr. Res. 1986, 153, 308.
(c) Shankar, B. B.; Kirkup, M. P.; McComble, S. W.;
Gangluy, A. K. Tetrahedron Lett. 1993, 34, 7171.
(18) Kiss, J.; D’Souza, R.; Taschner, P. Helv. Chim. Acta 1975, 58,
311.
Determination of enantiomeric ratio:20 µl of an 0.1M aqueous
solution of 5 was treated with 10 µl of a 1M aqueous solution
of (S)-(-)-1-phenylethylamine (pH 6.3 adjusted with
hydrochloric acid in advance) in an Eppendorf cap, which was
sealed and heated to 90 °C for 10 min. 90 mg of NaBH3CN
were dissolved in 300 µl of H2O and 4.5 µl of that solution
added to the reaction mixture. It was kept at 90 °C for 60 min,
diluted with 60 µl of H2O and injected for capillary
electrophoresis analysis (capillary: 77 cm, ID = 50 µm;
injection time: 2 sec; buffer: 50mM borate pH 10.3/23%
MeCN; 30 kV).
(19) Noe, C. R.; Freissmuth, J. Chromatogr., A 1995, 704, 503.
(20) Experimental:
1,2-O-(1-methylethylidene)-a-D-ribo-pentodialdo-1,4-
furanose 3: 15.0 g (70.13 mmol) NaIO4 was added to a
solution of 6.60 g (30.0 mmol) of 2 and 3 g NaHCO3 in 300
ml H2O within 10 min. After stirring at r. t. for 100 min, the
reaction mixture was concentrated (< 40 °C), the residue
extracted four times with 200 ml EtOAc, filtered, and the
combined filtrates concentrated. The residue was treated with
5 ml CCl4 and evaporated to dryness: 5.58 g (98%) 3.
Colorless foam. TLC (silica gel, EtOAc/MeOH 4:1): Rf 0.55.
1H NMR (200 MHz, D2O):1.32, 1.5 (2s, Me); 3.82 (dd,
(21) Miculka, C.; Eschenmoser, A. Helv. Chim. Acta in
preparation.
Article Identifier:
1437-2096,E;1999,0,S1,0948,0950,ftx,en;W00999ST.pdf
Synlett 1999, S1, 948–950 ISSN 0936-5214 © Thieme Stuttgart · New York