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A new class of monosaccharide derivatives: O-phthalimidohexoses
Gzrbohydrate Research, ClSC16 0 ElsevierScientificPublishing Company, Amsterdam - Printed in 3elgium
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Preliminary communication A new class of monosaccharide derivatives: O-phthalimidohexoses
EDWARD GROCHOWSKI and
JANUSZ JURCZAK
InstituteofOrganicChemistry,
PO&~ AcudemyofSriences,Ol-224
(ReceivedJune
W~TS~UU(pohnd)
28th, 1976; accepted for publication, July 2nd, 1976)
We recently reported that the use of Nhydroxyphthalimide as a nucleophilic reagent in reactions with alcohols in the presence of triphenylphosphine and diethyl azodicarboxylate leads to Gall@ derivatives of hydroxylamine’ _We now report on the application of this reaction to carbohydrate derivatives containing an “isolated” hydroxyl group to afford a new type of monosaccharide derivative, namely O-amino sugars. Treatment of 1,2:3,4-di-U-isopropylidene&-D-galactopyranose’ with equimolar amounts of Nhydroxyphthalimide, triphenylphosphine, and diethyl azodicarboxylate in tetrahydrofuran at room temperature for 24 h, followed by concentration, and chromatography of the residue on a silica gel column with benzene-ether (9: l), gave 1,2:3,4diU-isopropylidened-Ckphthalimidoiu-D-galactopyranose (I, 543%), m.p. 121--122O; V= 1615,174O and 1795 (C=O), and 700 cm-’ (aromatic); no OH absorption. The p.m.r. spectrum (chloroform+ was similar to that for 6deoxy-1,2:3,4-
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di-Uisopropyli~ene-6-phthalimido&Dgalactopyranose3 except for the chemical shift of H-6,6’. similarly, ethyl 2,3-dideoxy-at-D-e~tx-2-enopyranoside4 with 2 moles of each reagent for 1 mole of sugar gave ethyl 2,3_dideoxy4,6&0-phthalimido~-D-threuhex-2enopyranoside (2,78.5%), m-p. 250-252”, v*& 1615,174O and 1790 (C=C& and 695 cm’* (aromatic). The pms. spectrum (pyridine-d5) was similar to that for ethyl 2,3,4,6-tetradeoxy4,6-diphth&mid~-D-f~~eu-hex-2-enopyranoside3 ; the coupling constants for H-4 @a,4 5.0, J4,s 3.5 Hz) showed that inversion of configuration at C-4 bad occurred in this reaction. 23:5,6-IX-0isopropylidene-D-mannofuranoses was converted into two products that were isolated by chromatography on silica gel. The first wasN-(2,3:5,6diU-isopropyl idene-&D-mannofiuaosyloxy)phthalimide (3,ll .O%),m-p. 128-129O; rtfBna:1610,174O and 1795 (c----O), and 695 cm-’ (aromatic). The p.m.r. spectrum (chloroform&) was similar to that recorded for N-(2,3:5,&ii-0-isopropylidene~-D-mannofuranosyl)phthalimide6 _ The &configuration of this compound was established on the basis of the coupling constant .&,a --O JZL The second product wasN_(2,3:5,6did)-isopropylidene-& D-mannofuranosyloxy)phthalimide (4,65.0%), m.p. 146-147O; P”,: 1615,174O and 1795 (C=O), and 700 cm-’ (aromatic). The &configuration followed from the coupling constant &,a 4.0 Hz. The new compounds described here had correct elemental analyses, and apparently constitute the first examples of carbohydrate aderivatives of hydroxylamine. ACKNOWTXDGMENT The authors thank Professor A. Zamojski for his kind interest in this research. REFERENCES 1 E. Grochowski andJ. Jurczak,Synrhesff, in press. 2 R S. Tipson,Methods Gzrbohyd c&m, 2 (1963) 247. 3 W-k Szarek,C Depew,A. Zzmojski,and J- Jurczak,unpublkheddata_
4 R 3. Ferrierand N. Frasad,J. Brem Sot. C (1969) 570-575. 5 0. T. Schmidt,Merkods Ckbohyd C&m., 2 (1963) 319. G J. Jurczak,G. Grynkiewicz, and A. Zamojski,CirrMzy~? Res, 39 (1975) 147-150.
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Preliminary communication A new class of monosaccharide derivatives: O-phthalimidohexoses
EDWARD GROCHOWSKI and
JANUSZ JURCZAK
InstituteofOrganicChemistry,
PO&~ AcudemyofSriences,Ol-224
(ReceivedJune
W~TS~UU(pohnd)
28th, 1976; accepted for publication, July 2nd, 1976)
We recently reported that the use of Nhydroxyphthalimide as a nucleophilic reagent in reactions with alcohols in the presence of triphenylphosphine and diethyl azodicarboxylate leads to Gall@ derivatives of hydroxylamine’ _We now report on the application of this reaction to carbohydrate derivatives containing an “isolated” hydroxyl group to afford a new type of monosaccharide derivative, namely O-amino sugars. Treatment of 1,2:3,4-di-U-isopropylidene&-D-galactopyranose’ with equimolar amounts of Nhydroxyphthalimide, triphenylphosphine, and diethyl azodicarboxylate in tetrahydrofuran at room temperature for 24 h, followed by concentration, and chromatography of the residue on a silica gel column with benzene-ether (9: l), gave 1,2:3,4diU-isopropylidened-Ckphthalimidoiu-D-galactopyranose (I, 543%), m.p. 121--122O; V= 1615,174O and 1795 (C=O), and 700 cm-’ (aromatic); no OH absorption. The p.m.r. spectrum (chloroform+ was similar to that for 6deoxy-1,2:3,4-
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di-Uisopropyli~ene-6-phthalimido&Dgalactopyranose3 except for the chemical shift of H-6,6’. similarly, ethyl 2,3-dideoxy-at-D-e~tx-2-enopyranoside4 with 2 moles of each reagent for 1 mole of sugar gave ethyl 2,3_dideoxy4,6&0-phthalimido~-D-threuhex-2enopyranoside (2,78.5%), m-p. 250-252”, v*& 1615,174O and 1790 (C=C& and 695 cm’* (aromatic). The pms. spectrum (pyridine-d5) was similar to that for ethyl 2,3,4,6-tetradeoxy4,6-diphth&mid~-D-f~~eu-hex-2-enopyranoside3 ; the coupling constants for H-4 @a,4 5.0, J4,s 3.5 Hz) showed that inversion of configuration at C-4 bad occurred in this reaction. 23:5,6-IX-0isopropylidene-D-mannofuranoses was converted into two products that were isolated by chromatography on silica gel. The first wasN-(2,3:5,6diU-isopropyl idene-&D-mannofiuaosyloxy)phthalimide (3,ll .O%),m-p. 128-129O; rtfBna:1610,174O and 1795 (c----O), and 695 cm-’ (aromatic). The p.m.r. spectrum (chloroform&) was similar to that recorded for N-(2,3:5,&ii-0-isopropylidene~-D-mannofuranosyl)phthalimide6 _ The &configuration of this compound was established on the basis of the coupling constant .&,a --O JZL The second product wasN_(2,3:5,6did)-isopropylidene-& D-mannofuranosyloxy)phthalimide (4,65.0%), m.p. 146-147O; P”,: 1615,174O and 1795 (C=O), and 700 cm-’ (aromatic). The &configuration followed from the coupling constant &,a 4.0 Hz. The new compounds described here had correct elemental analyses, and apparently constitute the first examples of carbohydrate aderivatives of hydroxylamine. ACKNOWTXDGMENT The authors thank Professor A. Zamojski for his kind interest in this research. REFERENCES 1 E. Grochowski andJ. Jurczak,Synrhesff, in press. 2 R S. Tipson,Methods Gzrbohyd c&m, 2 (1963) 247. 3 W-k Szarek,C Depew,A. Zzmojski,and J- Jurczak,unpublkheddata_
4 R 3. Ferrierand N. Frasad,J. Brem Sot. C (1969) 570-575. 5 0. T. Schmidt,Merkods Ckbohyd C&m., 2 (1963) 319. G J. Jurczak,G. Grynkiewicz, and A. Zamojski,CirrMzy~? Res, 39 (1975) 147-150.