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This compound was prepared by benzylation of 2-chloro-6-iodopurine, which was prepared from 2,6-dichloropurine by an exchange reaction with concentrated hydroiodic acid: Elion, G. B.; Hitchings, G. H. J. Am. Chem. Soc. 1956, 78, 3508. The position of halogens in the above paper was only estimated. Thus, the reaction described in Scheme 2 is also proof that the compound obtained from 2.6-dichloropurine by reaction with hydroiodic acid is 2-chloro-6-iodopurine and not isomeric 6-chloro-2-iodopurine.
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26
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33645956827
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note
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The outcome of the reaction with 1 equiv of RMgCl strongly depends on the reaction temperature. Thus, the reaction with iPrMgCl at -80 °C followed with addition of water at -80 °C affords exclusively 5, whereas the same reaction at higher temperatures gives mixtures of 5 and 7a in a different ratio. Interestingly, formation of 9-benzyl-6-iodopurine or 6-isopropyl-2-chloropurine was not observed. It suggests that a Cl/Mg exchange reaction is connected with the introduction of an alkyl group to the 6 position. However, all attempts to prepare 6-alkyl-2-chloro-9-benzylpurines as putative intermediates of the formation of 9 failed.
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0029052163
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31
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0037146041
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(a) Fürstner, A.; Leitner, A.; Méndez, M.; Krause, H. J. Am. Chem. Soc. 2002, 124, 13856.
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35
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33645918661
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note
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Preliminary results show that 2-magnesiated purines are stabilized by electron-donating substituents in the 6 position of purine nuclei.
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