9-[(1S,4R,5S)-5-(tert-butyldimethylsilyloxy)-4-(tert-butyldimethylsilyloxymethyl)-2-cyclohexenyl]adenine | 247587-59-3

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 咪唑并嘧啶类
• 英文名称: 9-[(1S,4R,5S)-5-(tert-butyldimethylsilyloxy)-4-(tert-butyldimethylsilyloxymethyl)-2-cyclohexenyl]adenine
• 英文别名: 9-[(1S,4R,5S)-5-[tert-butyl(dimethyl)silyl]oxy-4-[[tert-butyl(dimethyl)silyl]oxymethyl]cyclohex-2-en-1-yl]purin-6-amine
• CAS: 247587-59-3
• 化学式: C₂₄H₄₃N₅O₂Si₂
• 分子量: 489.809
• InChiKey: CUSMOUPTZKZSDK-QRVBRYPASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.94
• 重原子数：
  33
• 可旋转键数：
  8
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  88.1
• 氢给体数：
  1
• 氢受体数：
  6

反应信息

• 作为反应物：
  描述：

  9-[(1S,4R,5S)-5-(tert-butyldimethylsilyloxy)-4-(tert-butyldimethylsilyloxymethyl)-2-cyclohexenyl]adenine 在 甲苯 、 silica gel 、 methanol-dichloromethane 作用下， 以 Trifluoroacetic acid monohydrate 为溶剂， 反应 16.0h， 以5:1) to afford 36 (149 mg, 54% over two steps)的产率得到9-[(1S,4R,5S)-5-hydroxy-4-hydroxymethyl-2-cyclohexenyl]adenine
  参考文献：
  名称：

  CARBOCYCLIC NUCLEOSIDES AND PROCESS FOR OBTAINING SUCH

  摘要：

  本发明提供了一种六元环的、至少部分不饱和的碳环核苷化合物，包括（-）对映体、（+）对映体和其药学上可接受的盐和酯。该化合物由公式（I）表示，其中Z代表六元环环中的一个双键，B是一个杂环，例如嘧啶或嘌呤碱基，X是一个叠氮基、氟或OR2，R1和R2相同或不同，表示相同或不同的保护基、氢、烷基、烯基、酰基或磷酸酯基团，其中烷基基团是一个饱和的、可选地未取代的含有1至20个碳原子的碳氢化合物，烯基基团是烷基基团的不饱和同系物，酰基是烷酰基或芳酰基。

  公开号：

  US20080176813A1
• 作为产物：
  描述：

  (1R,2S,3S,5S)-5-benzyloxy-3-(tert-butyldimethylsilyloxy)-2-(tert-butyldimethylsilyloxymethyl)cyclohexanol 在 palladium on activated charcoal manganese(IV) oxide 、 sodium tetrahydroborate 、 cerium(III) chloride 、 甲酸铵 、 三乙胺 、 三苯基膦 、 偶氮二甲酸二乙酯 作用下， 以 1,4-二氧六环 、 甲醇 、 二氯甲烷 为溶剂， 反应 44.0h， 生成 9-[(1S,4R,5S)-5-(tert-butyldimethylsilyloxy)-4-(tert-butyldimethylsilyloxymethyl)-2-cyclohexenyl]adenine
  参考文献：
  名称：

  Enantioselective Synthesis and Conformational Study of Cyclohexene Carbocyclic Nucleosides

  摘要：

  Enantioselective synthesis of a new family of unsaturated six-membered carbocyclic nucleosides using (R)-(-)-can one as starting material is described. Introduction of the base moiety via Mitsunobu reaction proceeded regio- and stereoselectively and with good chemical yield, while the Pd-coupling approach failed. H-1 NMR study and molecular modeling show the adenine compound exists in an equilibrium of H-3(2) and H-2(3) conformers (ratio 7:3) in favor of the 3'-endo half-chair conformation, with the base oriented in a pseudoaxial position. This conformational preference can be explained by the pi --> sigma*(C1')-(N1) interaction involving the antibonding orbital of the C1'-N bond.

  DOI：

  10.1021/jo9908288

文献信息

• CARBOCYCLIC NUCLEOSIDES AND PROCESS FOR OBTAINING SUCH
  申请人：Stichting REGA V.Z.W.

  公开号：EP1210347B1

  公开（公告）日：2004-06-23
• Enantioselective Synthesis and Conformational Study of Cyclohexene Carbocyclic Nucleosides
  作者：Jing Wang、Piet Herdewijn

  DOI：10.1021/jo9908288

  日期：1999.10.1

  Enantioselective synthesis of a new family of unsaturated six-membered carbocyclic nucleosides using (R)-(-)-can one as starting material is described. Introduction of the base moiety via Mitsunobu reaction proceeded regio- and stereoselectively and with good chemical yield, while the Pd-coupling approach failed. H-1 NMR study and molecular modeling show the adenine compound exists in an equilibrium of H-3(2) and H-2(3) conformers (ratio 7:3) in favor of the 3'-endo half-chair conformation, with the base oriented in a pseudoaxial position. This conformational preference can be explained by the pi --> sigma*(C1')-(N1) interaction involving the antibonding orbital of the C1'-N bond.
• Enantioselective Synthesis and Conformational Analysis of Cyclohexene Carbocyclic Nucleosides
  作者：Jing Wang、Piet Herdewijn

  DOI：10.1080/15257779908041505

  日期：1999.4

  An enantioselective approach towards the synthesis of optically pure cyclohexene nucleosides 3 has been developed starting from (R)-carvone. The key steps are the regio- and stereoselective hydroboration of an exo double bond, the selective reduction of an enone intermediate and introduction of a base moiety by Mitsunobu reaction. Conformational analysis showed that the adenine base adopts predominantly in a pseudo-axial position.