Reaction of 5,6-cyclic sulfates derived from glycofuranoses with bases. A one-pot synthesis of 6-deoxy-hexofuranos-5-ulose derivatives

Article abstract of DOI:10.1016/S0040-4039(99)02158-9

Methyl 2,3-O-isopropylidene-5,6-O-sulfuryl-α-D-mannofuranoside 1 reacted with nitrogen bases to give the corresponding aminosulfates. Strong bases such as sodium tert-butoxide or n-butyllithium afforded methyl 6-deoxy- 2,3-O-isopropylidene-α-D-lyxo-hexofuranos-5-uloside 7. The reaction was optimized with sodium tert-butoxide and applied to three other 5,6-cyclic sulfates derived from aldofuranosides to give the corresponding keto-aldoses in good yields. (C) 2000 Elsevier Science Ltd.

Full text of DOI:10.1016/S0040-4039(99)02158-9

TETRAHEDRON
LETTERS
Pergamon
Tetrahedron Letters 41 (2000) 659–662
Reaction of 5,6-cyclic sulfates derived from glycofuranoses with
bases. A one-pot synthesis of 6-deoxy-hexofuranos-5-ulose
derivatives
Thierry Gourlain, Anne Wadouachi ∗ and Daniel Beaupère
Laboratoire de Chimie Organique, Université de Picardie Jules Verne, 33 rue Saint-Leu 80039 Amiens, France
Received 16 September 1999; accepted 12 November 1999
Abstract
Methyl 2,3-O-isopropylidene-5,6-O-sulfuryl-α-D-mannofuranoside 1 reacted with nitrogen bases to give the
corresponding aminosulfates. Strong bases such as sodium tert-butoxide or n-butyllithium afforded methyl 6-
deoxy-2,3-O-isopropylidene-α-D-lyxo-hexofuranos-5-uloside 7. The reaction was optimized with sodium tert-
butoxide and applied to three other 5,6-cyclic sulfates derived from aldofuranosides to give the corresponding
keto-aldoses in good yields. © 2000 Published by Elsevier Science Ltd. All rights reserved.
The cyclic sulfates of vic-diols are well known and have been used as electrophiles in a variety of
nucleophilic displacement reactions.1 Such sulfates are obtained by catalytic oxidation of cyclic sulfites
with ruthenium trichloride and sodium periodate.2
We have already reported the regioselective synthesis of 6-O-alkyl and 6-alkynyl-6-deoxy compounds
via a 5,6-cyclic sulfate derived from mannofuranose. This method has been extended to pseudo-di or
trisaccharides and pseudo-C-disaccharides.3–5
More recently, it has been shown that 1,2-O-sulfuryldecane failed to generate C–C bonds with
some carbon nucleophiles. For example, 1,2-O-sulfuryldecane reacted with n-butyllithium to give,
unexpectedly, dodecanal in 99% yield.6
We herein report on the reactivity of 5,6-cyclic sulfates of glycofuranoses towards various organic and
inorganic bases.
The results of the reaction of methyl 2,3-O-isopropylidene-5,6-O-sulfuryl-α-D-mannofuranoside 13
with bases are illustrated in Table 1.
As expected, the use of weak bases such as pyridine (entry 1), triethylamine (entry 2) or DBU (entry
3), gave the corresponding aminosulfates 2,7 38 and 49 in quantitative yields. Similarly, reactions with
strong nitrogen bases such as sodium amide (entry 5) and LDA (entry 6) with the 5,6-cyclic sulfate 1 also
gave the expected substitution products 510 and 6,11 respectively (Scheme 1).
∗
Corresponding author. Fax: +33 3 22 82 75 61; e-mail: anne.wadouachi@sc.u-picardie.fr (A. Wadouachi)
0040-4039/00/$ - see front matter © 2000 Published by Elsevier Science Ltd. All rights reserved.
PII: S0040-4039(99)02158-9
tetl 16086

660
Table 1
Reaction of the cyclic sulfate derivative 1 with basic reagents
Scheme 1.
In contrast, reaction of the 5,6-cyclic sulfate 1 with n-butyllithium (entry 7) followed by acidic
hydrolysis gave the ketone compound methyl 6-deoxy-2,3-O-isopropylidene-α-D-lyxo-hexofuranos-5-
uloside 712,13 in 40% yield and no substitution product was detected (Scheme 2). Some degradation of
the 5,6-cyclic sulfate 1 was observed which could explain the relatively low yield of 7.
The optimum yield (79%) obtained for the methyl hexofuranos-5-uloside compound 7 was when 1
reacted with sodium tert-butoxide (entry 4, Scheme 2). It was found that treatment with stronger bases
such as NaH and tert-BuLi resulted in degradation of 1 (Table 1). A mechanism for the formation of 7 is
given in Scheme 3.

661
Scheme 2.
Scheme 3.
It is proposed that base catalyses elimination and generates the olefin 1a which hydrolyses to the
ketone 7.
The generality of this reaction was exemplified by treatment of sodium tert-butoxide with the related
substrates 8,4 1014 and 1215 to give the ketones 916 (77%), 1117 (73%) and 1318 (72%), respectively
(Table 2).
Table 2
Reaction of 5,6-cyclic sulfate glycofuranoses with sodium tert-butoxide
In conclusion, we described a one-pot synthesis of manno, gluco and galactofurano-5-ulose deri-
vatives in 72–79% yields by treatment of corresponding 5,6-O-sulfuryl compounds with sodium tert-
butoxide. It is envisaged that 5,6-deoxy-5-oxo derivatives are potential precursors of aminosugars and
cyclitols.

662
References
1. Lohray, B. B. Synthesis 1992, 1035.
2. (a) Sharpless, K. B.; Kim, B. M. Tetrahedron Lett. 1989, 30, 655. (b) Sharpless, K. B.; Gao, Y.; Lohray, B. B. Tetrahedron
Lett. 1989, 30, 2623.
3. Gourlain, T.; Wadouachi, A.; Meslouti, A. E.; Uzan, R.; Beaupère, D. Carbohydr. Lett. 1996, 2, 143.
4. Gourlain, T.; Wadouachi, A.; Uzan, R.; Beaupère, D. J. Carbohydr. Chem. 1997, 16, 1089.
5. Gourlain, T.; Wadouachi, A. R.; Beaupère, D. Synthesis 1999, 290.
6. Hoye, T. R.; Crawford, K. B. J. Org. Chem. 1994, 59, 520.
7. Data for 2: 13C NMR (CDCl3) δ 148.9 (C-40), 147.9 (C-20, C-60), 130.4 (C-30, C-50), 116.1 (C(CH3)2), 109.1 (C-1), 86.3
(C-2), 81.4 (C-3), 81.1 (C-4), 77.0 (C-5), 62.7 (C-6), 56.6 (OCH3), 27.1, 25.7 (C(CH3)2).
8. Data for 3: 13C NMR (CDCl3) δ 112.3 (C(CH3)2), 106.5 (C-1), 84.1 (C-2), 81.2 (C-3), 79.7 (C-4), 68.8 (C-5), 56.3 (C-6),
54.3 (OCH3), 53.7 (3 CH2), 25.4, 23.4 (C(CH3)2), 7.1 (3 CH3).
9. Data for 4: 13C NMR (CDCl3) δ 170.1 (C-100), 115.9 (C(CH3)2), 108.7 (C-1), 86.1 (C-2), 82.3 (C-3), 81.8 (C-4), 77.1 (C-5),
57.4 (CH2), 57.1 (OCH3), 55.9 (CH2), 51.4 (C-6), 50.7 (C-90), 30.5 (2 CH2), 27.6 (CH2), 27.1, 25.5 (C(CH3)2), 24.8, 21.7
(CH2).
10. Data for 5: 13C NMR (D2O) δ 115.3 (C(CH3)2), 108.8 (C-1), 86.4 (C-2), 82.9 (C-3), 82.2 (C-4), 76.1 (C-5), 56.9 (OCH3),
51.7 (C-6), 27.7, 26.3 (C(CH3)2).
11. Data for 6: 13C NMR (CDCl3) δ 112.4 (C(CH3)2), 106.8 (C-1), 84.3 (C-2), 80.1 (C-3), 79.7 (C-4), 69.9 (C-5), 59.7 (C-6),
54.8 (OCH3), 44.8 (2 CH), 25.7 (C(CH3)2), 23.8 (C(CH3)2, 4 CH3).
12. Data for 7: IR: C_O (1719 cm−1); 1H NMR (CDCl3) δ 4.98 (s, 1H, H-1, J1,2 0), 4.94 (dd, 1H, H-3, J2,3 5.8, J3,4 4.1), 4.50
(d, 1H, H-2), 4.37 (d, 1H, H-4), 3.28 (s, 3H, OCH3), 2.19 (s, 3H, H-6a,b,c), 1.35 (s, 3H, C(CH3)2), 1.21 (s, 3H, C(CH3)2);
13C NMR (CDCl3) δ 204.2 (C-5), 113.0 (C(CH3)2), 107.4 (C-1), 84.8 (C-4), 84.2 (C-2), 80.7 (C-3), 54.8 (OCH3), 27.7
(C-6), 25.7, 24.5 (C(CH3)2).
13. Gourlain, T.; Wadouachi, A.; Beaupère, D. Carbohydr. Res. 1999, 324, 66.
14. Calvo-Flores, F. G.; Garcia-Mendoza, P.; Hernandez-Mateo, F.; Isac-Garcia, J.; Santoyo-Gonzalez, F. J. Org. Chem. 1997,
62, 3944.
15. Data for 12: 1H NMR (CDCl3) δ 7.38–7.30 (m, 5H, CH(Ph)), 5.84 (d, 1H, H-1, J1,2 3.8), 4.99 (m, 1H, H-5), 4.69 (d, 1H,
CH2(Bn)), 4.65 (d, 1H, H-2), 4.54–4.43 (m, 3H, CH2(Bn), H-6, H-60), 4.06 (t, 1H, H-4, J3,4 5.1, J4,5 5.1), 3.92 (d, 1H,
H-3), 1.52 (s, 3H, C(CH3)2), 1.35 (s, 3H, C(CH3)2); 13C NMR (CDCl3) δ 136.3 (Cipso), 128.7, 128.4, 128.1 (CH(Ph)), 114.6
(C(CH3)2), 105.3 (C-1), 84.8 (C-2), 81.5 (C-3), 81.1 (C-4), 79.9 (C-5), 72.3 (CH2(Bn)), 68.9 (C-6), 27.4, 26.7 (C(CH3)2).
16. Data for 9: IR: C_O (1721 cm−1); 1H NMR (CDCl3) δ 7.28 (m, 5H, CH(Ph)), 5.17 (s, 1H, H-1, J1,2 0), 4.99 (dd, 1H, H-3,
J2,3 5.7, J3,4 4.2), 4.65 (t, 2H, CH2(Bn)), 4.48 (d, 1H, H-2), 4.45 (d, 1H, H-4), 2.22 (s, 3H, H-6a,b,c), 1.38 (s, 3H, C(CH3)2),
1.23 (s, 3H, C(CH3)2); 13C NMR (CDCl3) δ 204.1 (C-5), 136.9 (Cipso), 128.4, 127.9 (CH(Ph)), 113.0 (C(CH3)2), 105.6
(C-1), 85.3 (C-4), 84.3 (C-2), 80.7 (C-3), 69.1 (CH2(Bn)), 27.8 (C-6), 25.7, 24.5 (C(CH3)2).
17. Data for 11: IR: C_O (1722 cm−1); 1H NMR (CDCl3) δ 7.32–7.18 (m, 5H, CH(Ph)), 6.04 (d, 1H, H-1, J1,2 3.5), 4.60–4.53
(m, 3H, H-3, H-4, CH(Bn)), 4.43 (d, 1H, CH2(Bn)), 4.23 (d, 1H, H-3, J3,4 3.6), 2.18 (s, 3H, H-6a,b,c), 1.43 (s, 3H, C(CH3)2),
1.28 (s, 3H, C(CH3)2); 13C NMR (CDCl3) δ 206.6 (C-5), 136.8 (Cipso), 128.4, 127.9 (CH(Ph)), 112.2 (C(CH3)2), 105.8 (C-1),
85.4 (C-2), 83.6 (C-3), 81.7 (C-4), 72.3 (CH2(Bn)), 29.6 (C-6), 26.8, 26.2 (C(CH3)2).
18. Data for 13: IR: C_O (1718 cm−1); 1H NMR (CDCl3) δ 7.27 (m, 5H, CH(Ph)), 5.97 (d, 1H, H-1, J1,2 3.8), 4.59–4.53 (m,
3H, H-2, CH(Bn)), 4.43 (s, 2H, H-3, H-4), 2.27 (s, 3H, H-6a,b,c), 1.35 (s, 3H, C(CH3)2), 1.24 (s, 3H, C(CH3)2); 13C NMR
(CDCl3) δ 207.2 (C-5), 137.0 (Cipso), 128.4, 127.9, 127.7 (CH(Ph)), 112.0 (C(CH3)2), 106.3 (C-1), 89.7 (C-4), 83.6 (C-2,
C-3), 71.8 (CH2(Bn)), 29.6 (C-6), 25.7, 25.6 (C(CH3)2).