Convenient synthesis of 3-amino-3-deoxy-D-ribose

Abstract

3-Amino-3-deoxy-D-ribose and D-ribose were prepared from a derivative of D-xylose. 1,2-0-Isopropylidene-5-0-triphenylmethyl-a-D-xylofuranose (2) was oxidized by dimethyl sulfoxide -acetic anhydride to 1,2-O-isopropylidene-5-O-triphenylmethyl-a-~-erythro-pentofuranos-3-uose (3). The oxime (4) of this 3-keto sugar derivative was reduced with lithium aluminium hydride to 3-amino-3-deoxy-l,2-0-isopropylidene-5-0-triphenylmethyl-a-D-ribofuranose (5), isolated as the acetamido derivative (6). Hydrolysis yielded 3-amino-3-deoxy-D-ribose hydrochloride. 3 was reduced by sodium borohydride to 1,2-0-isopropylidene-5-0-triphenylmethyl-a-D-ribofuranoe (7), which yielded D-ribose on hydrolysis.Canadian Journal of Chemistry, 46, 1586Chemistry, 46, (1968 In recent years many unusual amino and interest because it occurs in puromycin (2) and deoxy sugars have been identified as components in 3'-amino-3'-deoxyadenosine (3). Puromycin, of a number of antibiotic substances (1). One of which has been identified as 6-dimethylamino-9-these sugars, 3-amino-3-deoxy-D-ribose, is of For personal use only.NOTES furanosyl]purine (4), has become an important biochemical tool since its inhibitory effect on protein biosynthesis was demonstrated (5). Both nucleosides exhibit significant antitumor activity (6, 7) and 3-amino-3-deoxy-D-ribose has been described as an intermediate useful for the preparation of compounds antagonistic to vitamins B, and B,, (8). Numerous synthetic 3'-amino-3'-deoxynucleosides have been reported (9)(10)(11)(12)(13)(14).Several procedures have been published for the synthesis of 3-amino-3-deoxy-D-ribose. The first two are similar in principle. Ammonolysis of 2,3-anhydropentose derivatives yields intermediate 3-acetamido-3-deoxypentose compounds; the required configurational inversion of these is obtained by the attack of the acetamido group on a neighboring trans-methylsulfonate (15, 16). Another method (17) depends on the inversion which takes place when the p-tolylsulfonoxy group of 1,2 ;5,6-di -0-isopropylidene-3 -0 -ptolylsulfonyl-a-D-glucofuranose undergoes hydrazinolysis. Reduction of the hydrazino compound yields a derivative of 3-amino-3-deoxy-D-allose which is then converted to 3-amino-3-deoxy-D-ribose via periodate oxidation and borohydride reduction. A fourth procedure (18) is shorter and more direct than the others. Periodate oxidation of methyl P-D-xylopyranoside followed by treatment of the intermediate dialdehyde with nitromethane and sodium yields the sodium salt of methyl 3-aci-nitro-3-deoxy-P-D-ribopyranoside. This is converted to the free nitropentoside with potassium bisulfate and anhydrous sodium sulfate in a ball-mill. Methyl 3-amino-3-deoxy-P-D-ribopyranoside is obtained by hydrogenation of the nitropentoside with platinum catalyst in the presence of hydrochloric acid.The present commuilication reports a new and simple method for preparing 3-amino-3-deoxy-Dribose. 1,2-0-Isopropylidene-E-D-xylofuranose (I), readily obtained by hydrolysis of 1,2;3,5-di-0-isopr'opylidene-a-D-xylofuranose (19), was...

Synthesis of the Germination Stimulant 3‐Methyl‐2H‐furo[2,3‐c]pyran‐2‐one and Analogous Compounds from Carbohydrates

“…This requirement was satisfied in an efficacious manner by the regioselective tritylation of 1,2-O-isopropylidene--xylofuranose (6) (an inexpensive, commercially available substrate easily obtained from -xylose), which gave the alcohol 7 (Scheme 3). [9] Oxidation of 7, according to a literature procedure, returned the ketone 8. [9] Several attempts at Wittig olefination of 8 went unrewarded; however, adoption of the Horner-Wadsworth-Emmons methodology returned the desired (Z)-olefin 9 in high yield and in 19-fold excess of the undesired (E) isomer 10.…”

“…[9] Oxidation of 7, according to a literature procedure, returned the ketone 8. [9] Several attempts at Wittig olefination of 8 went unrewarded; however, adoption of the Horner-Wadsworth-Emmons methodology returned the desired (Z)-olefin 9 in high yield and in 19-fold excess of the undesired (E) isomer 10. Treatment of 9 with aqueous trifluoroacetic acid, in a rapid reaction, resulted in hydrolysis of the trityl ether and acetonide, lactonisation and rearrangement of the resulting hemiacetal (though not necessarily in that order) to give the butenolide 11 in excellent yield.…”

Esters phosphoriques, phosphonates et oxydes de phosphine dérivés de sucres. Communication préliminaire

“…Le traitement de l'kther triphenylmkthylique 4 [3] de 1 par le phosphorochloridate approprie fournit avec des rendements respectifs de 95 et 93% 5 (F. 108,5-109,5", Les analyses CICmentaires, les SM. et les donnees spectroscopiques (UV., IR., RMN.)…”

Synthèse d'acétals de désoxy‐3‐hydroxyamino‐3‐furannoses. Note de laboratoire

“…-Les citosucres bloques 1 [6], 2 [7] et 3 [8] ont ete convertis en oximes correspondantes 4, partiellement dtcrite [9], 5 [7] reactions a ete appliquee ri des derives di-0 -cyclopentylidene, plus faciles a debloquer en milieu acide. Ainsi, 12 a ete prepare a partir du glucose, oxyde en 13, dont l'oxime 14 a it6 reduite en 15 avec les rendements habituels.…”

“…R,0,23 (Et,O/hexane 1:l). : 7,6 (m,Ph,C);5,90 (d,J(1,2) = 3,7, H-C(1)); 5,45 (s, NH, OH); 4,65 (t, J(2,3) = 3,7, H-C(2)); 3,78 (ddd, J(4,Sa) = 5,3, J(3,4) = 5, J(4,5h) = 3,3, H-C(4)); 3,39 (dd, J(5a,5b) = 10,7, Hb-C(5)); 3,35 (dd, H-C(3)); 3,19 (dd, Ha-C(5)); 1,33, 1,50 (2s, Me&). I3C-RMN (50,3 MHz): 14333, 128,73, 127,83, 127,03 (Ph);112,41 (Me2C); 104,78 (C(1)); 86,79 (Pb,C); 78,34 (C(2)); 77,02 (C(4)); 65,90 (C(3)); 63,89 (C(5)); 26,56 (Me&).…”