(2R,3R,3aS,9aR)-3-((tert-butyldimethylsilyl)oxy)-2-(((tert-butyldimethylsilyl)oxy)methyl)-3,3a-dihydro-2H-furo[2',3':4,5]oxazolo[3,2-a]pyrimidin-6(9aH)-one | 55264-11-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 二嗪类
• 英文名称: (2R,3R,3aS,9aR)-3-((tert-butyldimethylsilyl)oxy)-2-(((tert-butyldimethylsilyl)oxy)methyl)-3,3a-dihydro-2H-furo[2',3':4,5]oxazolo[3,2-a]pyrimidin-6(9aH)-one
• 英文别名: 3',5'-bis-O-(t-butyldimethylsilyl)-O²,2'-anhydro-1-(β-D-arabinofuranosyl)uracil；2,2'-anhydro-1-(3,5-di-O-t-butyldimethylsilyl-β-D-arabinofuranosyl)uracil；3',5'-bis-O-(tert-butyldimethylsilyl)-O²,2'-cyclouridine；3',5'-di-tert-butyldimethylsilyl-2,2'-anhydrouridine；(3aS)-3c-(tert-butyl-dimethyl-silanyloxy)-2t-[(tert-butyl-dimethyl-silanyloxy)-methyl]-(3ar,9ac)-2,3,3a,9a-tetrahydro-furo[2',3':4,5]oxazolo[3,2-a]pyrimidin-6-one；O^3'_,O5'-bis-(tert-butyl-dimethyl-silanyl)-arabino-2,2'-anhydro-uridine；(2R,4R,5R,6S)-5-[tert-butyl(dimethyl)silyl]oxy-4-[[tert-butyl(dimethyl)silyl]oxymethyl]-3,7-dioxa-1,9-diazatricyclo[6.4.0.02,6]dodeca-8,11-dien-10-one
• CAS: 55264-11-4
• 化学式: C₂₁H₃₈N₂O₅Si₂
• 分子量: 454.714
• InChiKey: JHDVYQOXUJWMKI-NRSFXHEJSA-N

物化性质

• 沸点：
  449.2±55.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.31
• 重原子数：
  30
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.81
• 拓扑面积：
  69.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (2R,3R,3aS,9aR)-3-((tert-butyldimethylsilyl)oxy)-2-(((tert-butyldimethylsilyl)oxy)methyl)-3,3a-dihydro-2H-furo[2',3':4,5]oxazolo[3,2-a]pyrimidin-6(9aH)-one 在 lithium aluminium tetrahydride 、 三乙胺 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 29.17h， 生成 1-[3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-D-erythro-pento-1-enofuranosyl]uracil
  参考文献：
  名称：

  Selenoxide elimination for the synthesis of unsaturated-sugar uracil nucleosides

  摘要：

  Introduction of a phenylseleno group to the sugar portion of uracil nucleosides and selenoxide elimination reactions of the resulting selenium-containing derivatives are described. A phenylselenide anion prepared by reducing (PhSe)2 with LialH4 was found to be highly reactive. By using this selenide as a nucleophile, ring openings of various types of cyclonucleosides and nucleosides having an anhydro structure in the sugar portion were accomplished. The products, which contain a phenylseleno group in the sugar portion, were oxidized with m-CPBA in CH2Cl2, and their susceptibility to the selenoxide elimination and regiochemistry of the reaction was investigated.

  DOI：

  10.1021/jo00018a038
• 作为产物：
  描述：

  尿嘧啶核苷 在 咪唑 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 7.0h， 生成 (2R,3R,3aS,9aR)-3-((tert-butyldimethylsilyl)oxy)-2-(((tert-butyldimethylsilyl)oxy)methyl)-3,3a-dihydro-2H-furo[2',3':4,5]oxazolo[3,2-a]pyrimidin-6(9aH)-one
  参考文献：
  名称：

  合成 2'-氨基尿苷衍生物作为 Diels-Alder 反应的有机催化剂

  摘要：

  摘要 为了开发一种基于核糖核苷骨架的新型不对称有机催化剂，我们设计并合成了 2'-氨基尿苷衍生物。合成的2'-氨基尿苷在碱基和糖部分都具有大取代基，可以催化肉桂醛和环戊二烯之间的Diels-Alder反应。然而，所得产物的光学纯度出乎意料地低。

  DOI：

  10.1080/15257770.2019.1646917

文献信息

• Synthesis of novel C-2 substituted pyrimidine nucleoside analogs
  作者：Martin Dunkel、P. Dan Cook、Oscar L. Acevedo

  DOI：10.1002/jhet.5570300540

  日期：1993.10

  A series of 2-(2-oxoalkylidene)-4(1H)-pyrimidinone nucleoside analogs were synthesized by the addition of the lithium enolates of methylketones to 2,5′- and 2,2′-anhydrouridines and to 2,5′-anhydrothymidines. Alternatively, 2-thiouridine was alkylated with bromomethyl ketones to yield 2-(2-oxoalkyl)thio-4(1H)-pyrimidinone ribofuranosides in good yields. These intermediates were subsequently transformed

  通过向2,5'-和2,2'-脱水尿苷中添加甲基酮的烯醇锂，合成了一系列2-（2-氧代亚烷基）-4（1 H）-嘧啶酮核苷类似物。 -脱水胸苷。或者，将2-硫代尿苷与溴甲基酮烷基化，以良好的产率得到2-（2-氧代烷基）硫基-4（1H）-嘧啶酮呋喃糖苷。这些中间体随后通过Eschenmoser硫磺挤出反应转化为标题化合物。2-（2-氧代亚烷基）-4-（1 H）-嘧啶酮核苷类似物在其1中显示烯醇质子信号H nmr光谱表明N-3与酮氧之间存在氢键。这些结构提供了具有沃森-克里克氢键潜力的官能团。
• Synthesis of a Protected <i>keto</i>-Lysidine Analogue via Improved Preparation of <i>Arabino</i>-isoCytosine Nucleosides
  作者：Joseph B. Sweeney、Paul A. Bethel、Duncan M. Gill、Agata M. Ochocińska、Anthony E. J. Walsh、Scarlett M. Walton

  DOI：10.1021/acs.orglett.9b00086

  日期：2019.4.5

  reactions has been developed, using microwave irradiation, significantly reducing reaction time and allowing facile access to a diverse range of novel nucleosides on the gram scale. The method has been used to prepare a precursor to a novel analogue of lysidine, a naturally occurring iminonucleoside found in tRNA.

  脱水尿苷与脂族胺反应生成N-烷基异胞嘧啶，但已报道的方法通常需要非常长的反应时间，并且收率低，范围狭窄。已经开发出一种用于此类反应的改进方法，该方法使用微波辐射，从而显着减少了反应时间，并允许以克为单位轻松获得各种新型核苷。该方法已用于制备赖氨酸新类似物的前体，赖氨酸是在t RNA中发现的天然亚氨基核苷。
• Cleavage of Cyclic Ethers Including Oxetane and Oxolane with a Highly Nucleophilic Species of Phenylselenide Anion
  作者：Kazuhiro Haraguchi、Hiromichi Tanaka、Hiroyuki Hayakawa、Tadashi Miyasaka

  DOI：10.1246/cl.1988.931

  日期：1988.6.5

  Phenylselenide anion generated from (PhSe)2 and LiAlH4, was found to be highly reactive to various types of cyclic ethers, providing a new method to prepare γ- and δ-phenylselenenyl alcohols from oxetane and oxolane, respectively.

  发现由 (PhSe)2 和 LiAlH4 生成的苯硒阴离子对各种类型的环醚具有高度反应性，为分别从氧杂环丁烷和氧杂环戊烷制备 γ- 和 δ- 苯基硒醇提供了一种新方法。
• Selective 5′-desilylation of 3′,5′-disilyi AraU derivatives under basic conditions
  作者：Loïc Le Hir de Fallois、Jean-Luc Décout、Marc Fontecave

  DOI：10.1016/0040-4039(95)02072-1

  日期：1995.12

  3′,5′-di-tert-butyldimethylsilyl-2,2′-anhydrouridine 3 was hydrolyzed under basic conditions to yield selectively 3′-tert-butyldimethylsilylarabinouridine 5 in 85 % yield. 3′,5′-disilyl-arabinouridine derivatives 4 and 6 also led selectively to 5 under the same conditions. These reactions suggest an intramolecular participation of the 2′-hydroxyl group in the desilylation and can be used to prepare

  3'，5'-二-叔丁基二甲基-2,2'-脱水尿苷3在碱性条件下水解得到选择性3'-叔-butyldimethylsilylarabinouridine 5以85％的产率。在相同条件下，3'，5'-二甲硅烷基-阿拉伯尿苷衍生物4和6也选择性地产生5。这些反应表明2'-羟基在脱甲硅烷基化中的分子内参与，并且可以用于快速且高产率地制备3'-硅烷基araU衍生物。
• Nucleic acid related compounds. 13
  作者：Morris J. Robins、E.M. Trip

  DOI：10.1016/s0040-4039(01)91909-4

  日期：1974.1