1340
LETTERS
SYNLETT
13
1,2;3,4-Di-O-isopropylidene-D-erythronic acid (4) - Solid chromium
trioxide (3.2 g, 32 mmoles) under nitrogen was added to a solution of
dry pyridine (5.2 mL) in dry dichloromethane (100 mL). The mixture
was stirred vigorously for 10 min and then a second solution of 2 (2 g,
6.9 mmoles) in dichoromethane (20 mL) was slowly added. The
reaction mixture was stirred for 48 h and then filtered on a silica gel
column and eluted with ethyl acetate. The filtrate was evaporated under
reduced pressure affording a brown oil. Toluene (2 x 50 mL) was added
to this oil and then evaporated under reduced pressure in order to
remove trace of acetic acid. The resulting brown solid was
chromatographed on a silica gel column and eluted with hexane/ethyl
4.55 (d, 1-H, J = 4.5 Hz, H-2), 4.49-4.41 (m, H-3 and H-4); C NMR
(75 MHz, CDCl ) δ (ppm) 178.7 (C-1), 71.2 (C-2), 73.7 (C-4), 70.4 (C-
3
+
3); LRFABMS m/z 119 [(M+1) , 28].
Acknowledgments
One of the authors (MNS) thanks CAPES-Brazil for a scholarship.
Financial supports from CNPq is fully acknowledged (VFF). We are
grateful to Professor Francis J. Schmitz (University of Oklahoma) for
EIMS and HRFABMS spectra.
o
acetate (7:3) yielding 4 as white solid (1.12 g, 75 %). mp 70-71 C;
References and Notes
3a
[α]D20 = -6.8 (c 0.66, CHCl ); [α]D20 lit. for enatiomer [α]2D0 = +7
3
-1
1
(1) (a) Bols, M. Carbohydrate Building Blocks; Jonh Wiley & Sons:
NY, 1996; (b) Gypser, A.; Peterek, M.; Scharf, H.-D., J. Chem.
Soc. Perkin Trans 1 1997, 1013; (c) Gypser, A.; Flasche, M.;
Scharf, H.-D. Liebigs Ann. Chem. 1994, 775.
(c 0.12 , CHCl ); IR (cm , KBr) 3500 (OH), 1750 (C=O); H NMR
3
(300 MHz, CDCl ) δ (ppm) 4.52 (d, 1-H, J = 3.6 Hz, H-2), 4.41(dt, 1-H,
3
J = 6.6 and 3.6 Hz, H-3), 4.08 (dd, 2-H, J = 6.6 and 0.6 Hz, H-4), 1.65,
13
1.57, 1.44 and 1.38 (4s, 12-H, 4Me); C (75 MHz, CDCl ) δ (ppm)
3
169.9 (C-1), 111.1 and 110.4 (CMe ), 74.8 (C-2), 73.9 (C-3), 64.4 (C-4),
26.6, 26.1, 25.9 and 25.1 (4Me); HRFABMS (M-15) 201.0775 (calcd =
201.0762).
(2) (a) Al-Hakin, A.H.; Haines, A.H.; Morley, C. Synthesis 1985, 207;
(b) Fujita, K.; Nakai, H.; Kobayashi, S.; Inoue, K.; Nojima, M.;
Ohno, M. Tetrahedron Lett. 1982, 23, 3511; (c) Valverde, S.;
Herradon, B.; Martin-Lomas, M. Tetrahedron Lett. 1985, 26,
3731.
2
+
N-Benzyl-3,4-O-isopropylidene-D-erythronamide (6) - A solution of
4 (500 mg, 2.31 mmoles), benzylamine (494 mg, 4.62 mmoles) in
toluene (5 mL) was refluxed for 9 h. The solution was evaporated under
reduced pressure forming a colorless oil which was dissolved in
dichloromethane (10 mL), extracted with 10% HCl solution (2 x 5 mL),
water (5 mL), and dried over anhydrous sodium sulfate. The solution
was evaporated and the residue chromatographed on a silica gel column
and eluted with hexane/ethyl acetate (7:3) yielding 6 as white solid (458
(3) (a) Untersteller, E.; Xin, Y.C.; Sinaÿ, P. Tetrahedron Lett. 1994,
35, 2537; (b) Veith, U.; Schwardt, O.; Jäger, V. Synlett 1996, 1181;
(c) Nicolaou, K.C.; Ramphal, J.Y.; Petasis, N.A.; Serham, C.N.I.
Angew. Chem. Int. Ed. Engl. 1991, 30, 1100; (d) Cohen, N.;
Banner, B.L.; Lopresti, R.J.; Wong, F.; Rosenberg; Liu, Y.-Y.;
Thom, E.; Libman, A.A. J. Am. Chem. Soc. 1983, 105, 3661; (e)
Ireland, R.; Wilcox, C.S.; Thaisrivong, S. J. Org. Chem. 1978, 43,
786.
o
-1
mg, 75 %). mp 67-68 C; [α]D20 = -12 (c 0.66, CHCl ); IR (cm , KBr)
3
1
3440 and 3320 (OH and NH), 1650 (C=O); H NMR (300 MHz,
CDCl ) δ (ppm) 7.38-7.26 (m, 5-H, Ph), 7.02 (bs, 1-H, NH), 4.58-4.45
3
(4) (a) Baxter, J.N.; Perlin, A.S. Can. J. Chem. 1960, 38, 2217; (b)
Hardegger, E.; Kreis, K.; Khadem, H.E. Helv. Chim. Acta. 1951,
34, 4163; (c) Mitchell, D.L. Can. J. Chem. 1963, 41, 214; (d)
MacDonald, D.L.; Crum, J.D.; Barker, R. J. Am. Chem. Soc. 1958,
80, 3379; (e) MacDonald, D.L.; Barker, R. J. Am. Chem. Soc.
1960, 82, 2301 (f) Gorin, P.A.J. Perlin, A.S. Can. J. Chem. 1955,
33, 1216; (g) Cohen, N.; Banner, B.L.; Laurenzano, A.J.; Carozza,
L. Org. Synth. 1984, 63, 127; (h) Abushsnab, E.; Bessodes, M.;
Antonakis, K. Tetrahedron Lett. 1984, 25, 3841; (i) Ballou, C.E. J.
Am. Chem. Soc. 1957, 79, 165.
(m, 2-H, CH Ph), 4.12 (dd, 1-H, J = 6.9 and 3.0 Hz, H-2), 4.28 (q, 1H, J
= 6.3 Hz, H-3), 4.10 (dd, 1-H, J = 8.7 and 6.3 Hz, H-4a), 3.99 (dd, 1-H,
2
J = 8.7 and 6.3 Hz, H-4b), 3.42 (d, 1-H, J = 3.0 Hz, OH), 1.45 and 1.37
13
(2s, 6-H, 2-Me); C NMR (75 MHz, CDCl ) δ (ppm) 170.9 (C-1),
3
137.6 (C-1’), 128.6, 127.4 and 127.3 (C-2’, C-3’, C-4’), 109.9 (CMe ),
2
75.9 (C-3), 70.6 (C-2), 66.0 (C-4), 43.2 (CH Ph), 26.5 and 24.9 (2Me);
2
+
HRFABMS (M+1) 266.1392 (calcd = 266.1392).
D-Erythronolactone (5)- A solution of 4 (1.63 g, 7.6 mmoles) in
methanol/ethyl acetate/water (1:1:1) was stirred at room temperature
during 8 days and then evaporated under reduced pressure to yield 5 as
o
4g
o
(5) Regeling, H.; de Rouville, E.; Chittenden, G.J.F. Recl. Trav. Chim.
Pays-Bas 1987, 106, 461.
white solid (896 mg, quantitative). mp 99-100 C (lit. 101-102 C);
4g
-1
[α]D20 -69.4 [c 0.5, H O; lit. [α]D20 -72 (c 0.5, H O)]; IR (cm , KBr)
3480 - 3200 (OH), 1770 (C=O); H NMR (300 MHz, CDCl ) δ (ppm)
2
2
1
(6) Garegg, P.J.; Samuelson, B., Carbohydr. Res. 1978, 67, 267.
3