2-Deoxyglucose, synthesis

This new multi-catalytic method shows a substantial improvement, from an economic as well as an environmental point of view, over traditional organic synthesis, as shown for the synthesis of the rare sugar 4-deoxyglucose (Table 13.2). 

Table 13.2 Benefits of the one-pot bio-chemo catalytic cascade as compared with the traditional step-wise stoichiometric organic synthesis of 4-deoxyglucose [27, 28].

Scheme 4. Solid-phase synthesis of the peptide-PAM ester 17 which served as an acyldonor in the subtilisin-catalysed segment condensation with glycopeptide fragment 18 (Ac3GlcNAc, 2-acetamido-3,4,6-tri-0-acetyl-2-deoxyglucose ...

Monodeoxygenation of 1,2- and 1,3-diols was achieved via their cyclic thiocarbonates, prepared from the diol and A/,A/ -thiocarbonyldiimidazole, by reaction with BusSnH-AIBN followed by alkaline hydrolysis (presumably, F would also be effective for the cleavage step). Equation (14) shows this process applied to synthesis of a derivative (73) of 5-deoxyglucose. Exclusive secondary deoxygenation is expected on the basis of radical stability in contrast, the derivative (72) was readily converted by an ionic process to an intermediate suitable for 6-deoxygenadon, since treatment with KI gave (74) quantitatively. 

Cassidy, P.J., and Kahan, EM., A stable enzyme-phosphoenolpyruvate intermediate in the synthesis of uridine-5 -diphospho-A-acetyl-2-amino-2-deoxyglucose 3-0-enolpyruvyl ether. Biochemistry, 12, 1364, 1973. 

F-2-fluoro-2-deoxyglucose (2-FDG) is normally produced in places where a cyclotron is locally available. Its molecular formula is CsHn FOs with molecular weight of 181.3 daltons. 18F-2-FDG can be produced by electrophilic substitution with 18F-fluorine gas or nucleophilic displacement with 18F-fluoride ions. The radiochemical yield is low with the electrophilic substitution, so the nucleophilic displacement reaction has become the method of choice for 18F-FDG synthesis. Deoxyglucose is labeled with 18F by nucleophilic displacement reaction of an acetylated sugar derivative followed by hydrolysis (Hamacher et al, 1986). In nucleophilic substitution, a fluoride ion reacts to fluorinate the sugar derivative. A solution of 1,3,4,6-tetra-O-acetyl-2-0-trifluoromethane-sulfonyl-/ -D-mannopyranose in anhydrous acetonitrile is added to a dry residue of 18F-fluoride containing aminopolyether (Kryptofix 2.2.2) and potassium carbonate (Fig. 8.1). Kryptofix 2.2.2 is used as a catalyst to enhance the reactivity of the fluoride ions. The mixture is heated... 

Figure 8.1. Schematic synthesis of 18F-2-Fluoro-2-deoxyglucose (FDG). (Reprinted with the permission of The Cleveland Clinic Center for Medical Art Photography 2009. All Rights Reserved)...

Kanamycin A, the oldest compound of this type, has been synthesised by two Japanese research groups. S. Umezawa and co-workers linked the protected 6-0-(3-amino-3-deoxy-a-D-glucopyranosyl)-2-deoxystreptainine (Table 2, 77) with the blocked glycosylchloride, prepared from 6-amino-6-deoxyglucose. Nakajiama and co-workers have reported the synthesis of kanamycin A from the protected 4-0-(6-amino-6-deoxy-a-D-glucopyranosyl)-2-deoxystreptamine (Table 2,80) and the tri-O-benzylglycosylchloride, obtained from 3-acetaniido-3-deoxy-glucose. 

H. Saeki and E. Ohki, 5,6-Epimino-D-glucofuranose and synthesis of nojirimycin (5-amino-5-deoxyglucose), Chem. Pharm. Bull, 16 (1968) 2477-2481. 

Seagar, M.J., Miguelis, R.D. Simon, C. (1980) Inhibitory Effects of Tunicamydn and 2-Deoxyglucose on Thyroglobulin Synthesis , European Journal of Biochemistry, 113, 91-6... 

The synthesis of dTDP-L-dihydrostreptose begins with the formation of dTDP-4-keto-6-deoxyglucose (Fig. 35, see also Fig. 31). 

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