Synthesis of Carba Analogues of Deoxy-4-C-(hydroxymethyl)pentofuranoses, Intermediates in the Synthesis of Carbocyclic Nucleosides

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Title:Synthesis of Carba Analogues of Deoxy-4-C-(hydroxymethyl)pentofuranoses, Intermediates in the Synthesis of Carbocyclic Nucleosides
Creators:
Hřebabecký, Hubert
Masojídková, Milena
Holý, Antonín
Journal or Publication Title:
Collection of Czechoslovak Chemical Communications, 63, 12, pp. 2044-2064
Uncontrolled Keywords:Cyclopentanes, Carbasugars, Pseudosugars, Carbocyclic pentofuranoses, Substituted 1,1-bis(hydroxymethyl)cyclopentanes, Carbocyclic nucleosides, Carbohydrates

Abstract

Racemic dimethyl 4-methoxy- (<strong>11 </strong>and <strong>12</strong>), diallyl 4-allyloxy- (<strong>13 </strong>and <strong>14</strong>) and dimethyl 4-(ethylsulfanyl)-2-hydroxycyclopentane-1,1-dicarboxylates (<strong>15 </strong>and <strong>16</strong>) were prepared by base-catalyzed addition of methanol, allyl alcohol and ethylsulfane, respectively, to dimethyl (4-oxobut-2-en-1-yl)malonate (<strong>6</strong>). Deallylation of <strong>13 </strong>and <strong>14 </strong>afforded 4-hydroxycyclopentanes <strong>27 </strong>and <strong>28</strong>. Reduction of <strong>11</strong>-<strong>16 </strong>with lithium aluminium hydride gave the corresponding 4-substituted 2,2-bis(hydroxymethyl)cyclopentanols. Dimethyl (2<i>S</i>,3<i>S</i>,4<i>R</i>)-, (2<i>R</i>,3<i>S</i>,4<i>R</i>)-3-benzyloxy-4-formyloxy-2-hydroxycyclopentane-1,1-dicarboxylates (<strong>35</strong>, <strong>36</strong>) and dimethyl (2<i>S</i>,3<i>S</i>,4<i>R</i>)-, (2<i>R</i>,3<i>S</i>,4<i>R</i>)-3-benzyloxy-2-benzoyloxy-4-methoxycyclopentane-1,1-dicarboxylates (<strong>39</strong>, <strong>40</strong>) were synthesized starting from D-glucose. Reduction of dimethyl cyclopentane-1,1-dicarboxylates <strong>39 </strong>and <strong>40 </strong>with lithium aluminium hydride, benzoylation of the formed hydroxy derivatives, hydrogenolysis of benzyl groups, conversion of the liberated hydroxy groups into dithiocarbonates and their reduction with tributylstannane afforded, after removal of the protecting groups, (2<i>R</i>,4<i>R</i>)-1,1-bis(hydroxymethyl)-4-methoxycyclopentan-2-ol ((2<i>R</i>,4<i>R</i>)-<strong>17</strong>) and (3<i>R</i>,4<i>R</i>)-1,1-bis(hydroxymethyl)-4-methoxycyclopentan-3-ol (<strong>51</strong>). Reduction of a mixture of esters <strong>35 </strong>and <strong>36 </strong>gave (2<i>R</i>,3<i>R</i>)-2-benzyloxy-5-(hydroxymethyl)hexane-1,3,6-triol (<strong>52</strong>) as the major product and (2<i>R</i>,3<i>S</i>,4<i>R</i>)-3-benzyloxy-1,1-bis(hydroxymethyl)cyclopentane-2,4-diol (<strong>53</strong>) as the minor product. The latter was converted into (3<i>R</i>,4<i>R</i>)-1,1-bis(hydroxymethyl)cyclopentane-3,4-diol (<strong>58</strong>). 3-Deoxycarba analogues <strong>51 </strong>and <strong>58 </strong>arose by migration of benzoyl group in the preparation of the dithiocarbonates.

Title:Synthesis of Carba Analogues of Deoxy-4-C-(hydroxymethyl)pentofuranoses, Intermediates in the Synthesis of Carbocyclic Nucleosides
Creators:
Hřebabecký, Hubert
Masojídková, Milena
Holý, Antonín
Uncontrolled Keywords:Cyclopentanes, Carbasugars, Pseudosugars, Carbocyclic pentofuranoses, Substituted 1,1-bis(hydroxymethyl)cyclopentanes, Carbocyclic nucleosides, Carbohydrates
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:63
Number:12
Page Range:pp. 2044-2064
ISSN:0010-0765
E-ISSN:1212-6950
Publisher:Institute of Organic Chemistry and Biochemistry
Related URLs:
URLURL Type
http://dx.doi.org/10.1135/cccc19982044UNSPECIFIED
ID Code:1444
Item Type:Article
Deposited On:06 Feb 2009 17:09
Last Modified:06 Feb 2009 16:09

Citation

Hřebabecký, Hubert; Masojídková, Milena; Holý, Antonín (1998) Synthesis of Carba Analogues of Deoxy-4-C-(hydroxymethyl)pentofuranoses, Intermediates in the Synthesis of Carbocyclic Nucleosides. Collection of Czechoslovak Chemical Communications, 63 (12). pp. 2044-2064. ISSN 0010-0765

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