2-Desoxy-D-ribose

Praparative Herstellung der 2-Desoxy-D-ribose, by E. Hardegger, M. Schellen-baum, R. Huwyler, and A. Ziist, Helv. Chim. Acta, 40 (1957) 1815-1818. 

Synthese von (-)-Muscarin aus 2-Desoxy-D-ribose. Synthese von Muscarin-ahnli-chen Verbindungen und ein neuer Konfigurationsbeweis fur Chitarsaure, by H. Furter... 

The composition and function of desoxyribonucleic acids have been studied extensively in recent years, and wider knowledge of the behavior of 2-desoxy-D-ribose became urgent. In this review developments in nucleic acid chemistry which have led to advances in our knowledge of 2-desoxypentoses (and vice versa) will be stressed. 

Desoxy-D-ribose occurs naturally as the carbohydrate component of desoxyribonucleic acids. From an examination by the ultraviolet chromatographic technique, of a range of nucleic acids isolated from animal, plant and bacterial sources, Chargaff and his coworkers10 have concluded that this sugar is the only 2-desoxypentose found so far to occur naturally in the nucleic acids. 

Until recently the lactol ring structure of 2-desoxy-D-ribose in nucleic acid had been proved conclusively only for the thymidine nucleoside component and in this case it was furanose in form.26 Subsequently Brown and Lythgoe,27 by application of the periodate oxidation procedure to the 2 -desoxy ribosides of guanine, hypoxanthine, cytosine and thymine, afforded proof of the presence of a furanose sugar in each compound. 

Fio, 1.—Curves for Light-absorption in the Dische Test (o) 2-Desoxy-D-ribose (61) D-Arabinal (i2) L-Arabinal (c) Furfuryl alcohol (d) w-Methoxylevulinaldehyde Dimethyl Acetal (e) Sodium Thymonucleate (/) Methyl 2-desoxy-/3-n-ribopyrano-side (g) Methyl 3,4-Dimethyl-2-desoxy-/3-L-ribopyranoside. 

It is apparent that a triose phosphate is the common intermediate between D-ribose and 2-desoxy-D-ribose in metabolism. 

Good yields are obtained at all stages of this synthesis of 2-desoxy-D-ribose, and for preparative purposes Sowden167 claims that the isolation of intermediates is unnecessary. The method would be a valuable one for the preparation of 2-desoxy-D-ribose if D-erythrose were obtainable in a pure state in large quantities. Overend and coworkers1 8 have investigated various methods for the preparation in bulk of this tetrose from easily accessible materials, but a completely satisfactory method is still required. 

Catalytic hydrogenation of LXVI in the presence of Raney nickel and calcium hydroxide afforded methyl 2-desoxy-/3-D-riboside (LXVII). This on hydrolysis with dilute acetic acid yielded 2-desoxy-D-ribose, which was isolated as the aniline 2-desoxy-D-riboside. Likewise dehalo-genation of LXV gave methyl 3-desoxy-/3-D-riboside (LXVIII). The position of the desoxy group in LXVIII was established by hydrolyzing it and hydrogenating the product. The resultant desoxypentitol and its tetrabenzoate were both optically inactive, indicating that the... 

Allerton and Overend180 showed that the action of hydrochloric acid on LXIV leads to a slightly better yield (18.4%) of the methyl 2-halogeno-2-desoxy-D-arabinoside, but these methods have no value for the large scale synthesis of 2-desoxy-D-ribose. 

Several general synthetic routes for the preparation of 2-desoxy-D-ribose have been described. 

Hough187 has outlined a novel method for the synthesis of 2-desoxy-D-ribose. An excess of allylmagnesium bromide was allowed to react with 2,3-isopropylidene-D-glyceraldehyde188 in ethereal solution and,... 

Another method for the preparation of 2-desoxy-D-ribose, using 2,3-isopropylidene-D-glyceraldehyde as an initial material has been outlined briefly by Overend and Stacey.106 The glyceraldehyde derivative was condensed with acetaldehyde in the presence of anhydrous potassium... 

In contrast to these results, reaction between 5,6-dimethylbenzimidaz-ole silver and l-chloro-3,4-diacetyl-2-desoxy-D-ribose in xylene solution at 100° readily gave a homogeneous 5,6-dimethylbenzimidazole-l (.3, 4/-diacetyl-2 -desoxy-D-ribopyranoside), hydrolysis of which furnished... 

Some phosphoric acid derivatives of 2-desoxy-D-ribose have been obtained by enzymic methods of preparation. A reaction analogous to the phosphorolysis of glycogen to D-glucose 1-phosphate241 has been effected with either hypoxanthine- or guanine-D-riboside, both of which could be split by enzymic phosphorolysis with the formation of D-ribose 1-phosphate.242 The successful conclusion of these experiments prompted similar investigations with desoxyribonucleosides. 

Manson and Lampen243 reported that they obtained the phosphorolysis and arsenolysis of hypoxanthine desoxyriboside by enzyme preparations from calf-thymus gland and rat liver. An acid-stable phosphate ester was isolated as a product of phosphorolysis. Results to be outlined suggested that this ester was 2-desoxy-D-ribose 5-phosphate and evidence was obtained for its formation by a mutase type reaction from 2-desoxy-D-ribose 1-phosphate. This evidence was extended and reinforced when Manson and Lampen244 obtained indications for the formation of desoxy-D-ribose 1-phosphate during the phosphorolysis of thymidine. Consequently the conversions outlined may be depicted as shown. 

Desoxy-D-ribose 1-phosphate + hypoxanthine 2-Desoxy-D-ribose 5-phosphate... 

Arsenolysis of hypoxanthine desoxy-D-riboside resulted in the formation of hypoxanthine and free 2-desoxy-D-ribose.248 Probably the primary product is 2-desoxy-D-ribose 1-arsenate, which decomposes in aqueous media to 2-desoxy-D-ribose and arsenate ions. 

Hartmann V, von Sonntag C, Schulte-Frohlinde D (1970)y-Radiolyse von 2-Desoxy-D-ribose in wass-riger Losung. Z Naturforsch 25b 1394-1404... 

Cleavage of the hydrazone with benzaldehyde as described by Meisenheimer and Jung gave D-eryfkro-2-desoxypentose ( 2-desoxy-D-ribose ), in 82 % yield... 

Kinetin (6-furfurylaminopurine) aroused interest because it has the ability to stimulate the cell division of certain plant seedlings. It has not been shown whether it is a genuine natural product, as it can be isolated from artificially altered desoxyribonucleic acid. This shows that it forms by the reaction of adenine with 2-desoxy-D-ribose.374,375... 

Synthetic 2-desoxy-L-ribose (-L-arabinose), prepared by the action of dilute sulfuric acid on L-arabinal (L-ribal), had the same numerical values of initial and equilibrium specific rotation (but opposite sign) as had the sugar of thymus nucleic acid. Hence the sugar was identified as 2-desoxy-D-ribose. On treatment with dilute sul-... 

The diphosphosugar should be studied further, since it offers the chance of identifying the sugar of the pyrimidine nucleosides of desoxy-ribosenucleic acid. There is every reason to believe that the sugar is 2-desoxy-D-ribose, but no definite proof is yet forthcoming. 

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