Nucleic Acid Related Compounds. 136. Synthesis of 2-Amino- and 2,6-Diaminopurine Derivatives via Inverse-Electron-Demand Diels-Alder Reactions

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Title:Nucleic Acid Related Compounds. 136. Synthesis of 2-Amino- and 2,6-Diaminopurine Derivatives via Inverse-Electron-Demand Diels-Alder Reactions
Creators:
Lin, Xiaoyu
Robins, Morris J.
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 71, 7, pp. 1029-1041
Uncontrolled Keywords:5-Aminoimidazoles, Curtius rearrangement, Purines, Nucleosides, Triazines, Diels-Alder inverse-electron-demand reactions

Abstract

Thermal inverse-electron-demand Diels-Alder reactions of 5-aminoimidazoles and 2,4,6-tris(ethoxycarbonyl)-1,3,5-triazine (<strong>2</strong>) with spontaneous retro-Diels-Alder loss of ethyl cyanoformate and elimination of ammonia give 2,6-bis(ethoxycarbonyl)purines. A report that selective alkaline hydrolysis followed by acid-catalyzed decarboxylation gave 6-(ethoxycarbonyl)purine products was not in harmony with known reactions in purine chemistry. Our reinvestigation has shown that the 6-(ethoxycarbonyl) group undergoes preferential base-promoted hydrolysis, as expected, but regioselectivity for attack of hydroxide at the carbonyl group at C6 is not high (relative to hydrolysis of both C2 and C6 esters). The structure of 9-benzyl-2-(ethoxycarbonyl)purine was determined by X-ray crystallography and confirmed by Curtius rearrangement of the azidocarbonyl analogue to give 2-amino-6-benzylpurine. Acid-catalyzed decarboxylation of the 2,6-dicarboxylate formed during hydrolysis gave 9-benzylpurine, and Curtius rearrangement of 2,6-bis(azidocarbonyl)-9-benzylpurine gave 2,6-diamino-9-benzylpurine. Attempted applications of inverse-electron-demand Diels-Alder reactions of <strong>2</strong> with nucleoside derivatives were problematic. <p>

Title:Nucleic Acid Related Compounds. 136. Synthesis of 2-Amino- and 2,6-Diaminopurine Derivatives via Inverse-Electron-Demand Diels-Alder Reactions
Creators:
Lin, Xiaoyu
Robins, Morris J.
Uncontrolled Keywords:5-Aminoimidazoles, Curtius rearrangement, Purines, Nucleosides, Triazines, Diels-Alder inverse-electron-demand reactions
Divisions:Life and Chemical Sciences > Institute of Organic Chemistry and Biochemistry > Collection of Czechoslovak Chemical Communications
Journal or Publication Title:Collection of Czechoslovak Chemical Communications
Volume:71
Number:7
Page Range:pp. 1029-1041
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc20061029UNSPECIFIED
ID Code:2522
Item Type:Article
Deposited On:06 Feb 2009 17:19
Last Modified:06 Feb 2009 16:19

Citation

Lin, Xiaoyu; Robins, Morris J. (2006) Nucleic Acid Related Compounds. 136. Synthesis of 2-Amino- and 2,6-Diaminopurine Derivatives via Inverse-Electron-Demand Diels-Alder Reactions. Collection of Czechoslovak Chemical Communications, 71 (7). pp. 1029-1041. ISSN 0010-0765

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