7- Glycosyl-purines

Conversion of L-fucosyl- and 3 -0-methyl-D-glycosyl-purines into nucleosides of two naturally occurring, rare sugars, 6-deoxy-L-talose and 3-O-methyl-D-mannose, could be achieved57 by stereospecific reduction at C-2 of 7-(6-deoxy-3,4-0-isopropylidene-/ -L-h/xo-hexopyranosyl-2-ulose)theophylline (35a) and 7-(4,6-0-benzylidene-3-0-methyl-/ -D-orobtno-hexopyranosyI-2-ulose)theophylline (8). Treatment of 35a and 8 with sodium borohydride in ethanol afforded the expected 7-(6-deoxy-3,4-0-isopropylidene-/ -L-talopyranosyI)theophylline (84) and 7-(4,6-... 

Nucleobase anion glycosylation of 6-substituted purines yields the jV -nucleosides as the main products. The situation changes if 5-aminoimidazole-4-carbonitrile instead of a purine is used as a precursor, then 4-amino-l-(ribofuranosyl)imidazole-5-carbonitrile (AICN-riboside) is formed as the main product and the N3 regioisomer as a minor component. For this reason imidazole nucleosides are very useful intermediates, especially for the synthesis of N7 glycosylated purines,... 

Although the method gives pure -D-anomers, N9 as well as N7 glycosylated purines 19 and 20 can be formed. When the reaction is performed with 6-methoxypurin-2-amine the N9 glycosylated compound is isolated as the major and the N7 glycosylated compound as the minor... 

Purine, 6-bromo-9-/3-D-(2,3,5-tri-0-acetyl)ribofuranosyl-synthesis, 5, 598 Purine, 6-carboxy-reactions, 5, 549 Purine, 8-carboxy-reactions, 5, 549 Purine, 2-chloro-reactions, 5, 561 synthesis, 5, 597 Purine, 6-chloro-alkylation, 5, 529 glycosylation, 5, 529 oxidation, 5, 539 3-oxides reactions, 5, 554 synthesis, 5, 595 reactions, 5, 561, 595 with ammonia, 5, 562 with fluorides, 5, 563 with trimethylamine, 5, 562 9- -D-ribofuranoside synthesis, 5, 560 synthesis, 5, 597, 598 Purine, 8-chloro-amination, 5, 542 Purine, 6-chloro-8-ethoxy-synthesis, 5, 591 Purine, 6-chloro-9-ethyl-dipole moment, 5, 522 Purine, 6-chloro-2-fluoro-riboside... 

Purine, 2,6-dithioxo-1,2,3,6-tetrahydro-dethiation, 5, 558 Purine, 8-ethoxy-synthesis, 5, 577, 596 Purine, 6-ethoxycarbonylmethyl-nucleoside synthesis, 5, 561 Purine, 8-ethoxy-7-methyl-synthesis, 5, 577 Purine, 9-ethyl-synthesis, 5, 593 Purine, 6-fonnyl-reactions, 5, 547 synthesis, 5, 593 Purine, 8-fonnyl-reactions, 5, 547 Purine, 2-fluoro-synthesis, 5, 597 Purine, 6-fluoro-alkylation, 5, 529 synthesis, 5, 563, 573 Purine, 6-fluoro-9-methyl-reactions, with ammonia, 5, 562 Purine, 6-furfurylamino- — see Kinetin Purine, 9-glycofuranosyl-synthesis, 5, 572 Purine, 2-glycosyl-synthesis, 5, 587 Purine, 8-glycosyl-synthesis, 5, 585 Purine, 9-glycosyl-synthesis, 5, 572 Purine, 8-halo-synthesis, 5, 598 Purine, 2-hydrazino-synthesis, 5, 593 Purine, 8-o -hydroxyethyl-synthesis, 5, 574... 

Purines, N-alkyl-N-phenyl-synthesis, 5, 576 Purines, alkylthio-hydrolysis, 5, 560 Mannich reaction, 5, 536 Michael addition reactions, 5, 536 Purines, S-alkylthio-hydrolysis, 5, 560 Purines, amino-alkylation, 5, 530, 551 IR spectra, 5, 518 reactions, 5, 551-553 with diazonium ions, 5, 538 reduction, 5, 541 UV spectra, 5, 517 Purines, N-amino-synthesis, 5, 595 Purines, aminohydroxy-hydrogenation, 5, 555 reactions, 5, 555 Purines, aminooxo-reactions, 5, 557 thiation, 5, 557 Purines, bromo-synthesis, 5, 557 Purines, chloro-synthesis, 5, 573 Purines, cyano-reactions, 5, 550 Purines, dialkoxy-rearrangement, 5, 558 Purines, diazoreactions, 5, 96 Purines, dioxo-alkylation, 5, 532 Purines, N-glycosyl-, 5, 536 Purines, halo-N-alkylation, 5, 529 hydrogenolysis, 5, 562 reactions, 5, 561-562, 564 with alkoxides, 5, 563 synthesis, 5, 556 Purines, hydrazino-reactions, 5, 553 Purines, hydroxyamino-reactions, 5, 556 Purines, 8-lithiotrimethylsilyl-nucleosides alkylation, 5, 537 Purines, N-methyl-magnetic circular dichroism, 5, 523 Purines, methylthio-bromination, 5, 559 Purines, nitro-reactions, 5, 550, 551 Purines, oxo-alkylation, 5, 532 amination, 5, 557 dipole moments, 5, 522 H NMR, 5, 512 pJfa, 5, 524 reactions, 5, 556-557 with diazonium ions, 5, 538 reduction, 5, 541 thiation, 5, 557 Purines, oxohydro-IR spectra, 5, 518 Purines, selenoxo-synthesis, 5, 597 Purines, thio-acylation, 5, 559 alkylation, 5, 559 Purines, thioxo-acetylation, 5, 559... 

More interesting are the substitution reactions on the triazole ring where a characteristically different course can be expected from that of analogous reactions in the purine series. These reactions were studied in more detail only in connection with the preparation of the glycosyl derivatives, and the experimental material does not permit the drawing of general conclusions. 

P212121 Z — 8 Dx= 1.57 R = 0.085 for 1,743 intensities. The two independent molecules have similar conformations. The glycosyl dispositions are anti (90.1°, 91.2°), and the D-ribosyl groups are 3T4 (24.0°, 34.1° 15.6°, 35.5°). The exocyclic, C-4 -C-5 bond orientations are gauche+ (63.1°, 53.8°). The orientation of the methyl groups in both molecules is such that it is directed away from the imidazole moiety of the base, that is, the 0-6-C-7 bond is trans to the C-5-C-6 bond this arrangement constitutes an obstacle to formation of Watson-Crick hydrogen-bonds to the complementary base cytosine. In molecule A, 0-6 and C-7 are displaced from the purine plane by 79 and 87 pm, and, in molecule B, by 49 and 16 pm. The bases are stacked. 

Sulfoxides have also been used in the synthesis of nucleoside analogs (Scheme 3.2). Chanteloup and Beau reported the synthesis of ribofuranosyl sulfoxide 13 and its use in the glycosylation of a series of silylated pyrimidine and purine bases.7 Although 16 is not an anomeric sulfoxide, its reaction with cytosine derivative 17 is conceptually related.8... 

Aspartic acid and arginines are important substrates for the biosynthesis of purine bases. They are also glycosylation sites in proteins. These reasons have been at the origin of the synthesis of their mono and difluoro analogues. 

The cytotoxicity of fluoroaspartic acids and of fluoroasparagines, their inhibition of the biosynthesis of purines and of the glycosylation of proteins, as well as the inhibition... 

A major recent growth point in substitution reactions has been the synthesis of pteridine glycosides, especially ribosides for study as probes in DNA chemistry taking advantage of the fluorescent properties of pteridines (see Section 10.18.12.4). Typically these reactions are developments of standard methods of glycosylation used with purines and pyrimidines as nucleophiles. In these and in other cases, the ambident nucleophiles within the pterin... 

Purine and pyrimidine nucleotides are essential for a vast number of biological processes such as the synthesis of RNA, DNA, phospholipids, glycogen, and the si-alylation and glycosylation of proteins. Both purines and pyrimidines can be synthesized de novo in mammalian cells through multistep processes. In addition to the de novo synthesis, purine nucleotides can also be synthesized via the salvage of... 

The base of a nucleotide is joined covalently (at N-l of pyrimidines and N-9 of purines) in an iV-/3-glycosyl bond to the 1 carbon of the pentose, and the phosphate is esterified to the 5 carbon. The AT-j3-glycosyl bond is formed by removal of the elements of water (a hydroxyl group from the pentose and hydrogen from the base), as in O-glycosidic bond formation (see Fig. 7-31). 

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