N-Benzoyl-N,9-bis(trimethylsilyl)adenin | 18055-47-5

• 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: N-Benzoyl-N,9-bis(trimethylsilyl)adenin
• 英文别名: Benzamide, N-(trimethylsilyl)-N-[9-(trimethylsilyl)-9H-purin-6-yl]-；N-trimethylsilyl-N-(9-trimethylsilylpurin-6-yl)benzamide
• CAS: 18055-47-5
• 化学式: C₁₈H₂₅N₅OSi₂
• 分子量: 383.6
• InChiKey: CAESNCKMRVIYKU-UHFFFAOYSA-N

物化性质

• 沸点：
  454.1±50.0 °C(Predicted)
• 密度：
  1.11±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.99
• 重原子数：
  26
• 可旋转键数：
  4
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  63.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-Benzoyl-N,9-bis(trimethylsilyl)adenin 在 trimethylsilyl trifluorosulfonate 、 氨 、 四氯化锡 作用下， 以 甲醇 、 乙腈 为溶剂， 反应 48.0h， 生成 9-(α-D-arabinofuranosyl)adenine
  参考文献：
  名称：

  Nucleotides. LXXIV Synthesis of a-D-Arabino-oligonucleotides

  摘要：

  The 5 alpha-D-arabinofuranosylnucleosides alpha-araU (15), alpha-araT (18), alpha-araC (22), alpha-araA (25), and alpha-araG (28) have been synthesized by the modified silyl-method. The amino groups at the nucleobases and the 2'-hydroxy group at the sugar moiety were protected by the 2-(4-nitro-phenyl) ethoxycarbonyl (npeoc) group (37-40) and the amide function in alpha-araG was additionally blocked by the 2-(4-nitrophenyl)ethyl group (63) to improve solubility in organic solvents. Mono-and dimethoxytritylation of the 5'-OH group was performed in the usual manner to give 41-48, 64, and 65 in high yields and further substitution of the 3'-OH group led to the monomeric building blocks 66-75 as well as the 3'-O-succinoyl derivatives 76-85 functioning as starting units in solid-support oligonucleotide synthesis. A large number of oligo-alpha-arabinonucleotides have been prepared on modified CPG-material applying the npeoc/npe strategy as a very efficient synthetic tool for highly purified, homogenous oligomers. Hybridizations between alpha-arabinonucleotide strands revealed in analogy to earlier findings an antiparallel orientation whereas the combination of an oligo-alpha-D-arabinonucleotide with a complementary oligo-2'-deoxy-beta-D-ribofuranosylnucleotide showed base-pairing only if a parallel polarity was present. The advantages in oligo-alpha-arabinonucleotide synthesis were furthermore demonstrated by the synthesis of the t alpha-ANA(his) a structural analog of the natural tRNA(his) of the phage T5.

  DOI：

  10.1080/15257770500267113
• 作为产物：
  描述：

  腺嘌呤 反应 6.17h， 生成 N-Benzoyl-N,9-bis(trimethylsilyl)adenin
  参考文献：
  名称：

  Visser, G. M.; van Westrenen, J.; van Boeckel, C. A. A., Recueil des Travaux Chimiques des Pays-Bas, 1986, vol. 105, p. 528 - 537

  摘要：

  DOI：
• 作为试剂：
  描述：

  (S)-[(2R,3R,4R)-3,4-Diacetoxy-5-bromo-2-((R)-1,2-diacetoxy-ethyl)-tetrahydro-furan-3-yl]-(2,2,2-trifluoro-acetylamino)-acetic acid methyl ester 在 N-Benzoyl-N,9-bis(trimethylsilyl)adenin 作用下， 以 二氯甲烷 为溶剂， 160.0 ℃ 、2.0 kPa 条件下， 反应 0.33h， 生成 2,3,5,6-tetra-O-acetyl-1,1¹-anhydro-3-C-(R)-(methoxycarbonyl)methyl-1-(R), 1¹(S)-N-trifluoroacetoepimino-β-D-allofuranose
  参考文献：
  名称：

  多恶英核苷部分类似物的合成

  摘要：

  摘要在无水N，N-二甲基甲酰胺中存在乙酸铵的情况下，在1,2：5,6-二-O-异亚丙基-α-d-核糖-六呋喃糖-3-ulose中添加硝基乙酸甲酯，得到1,2：5 ，6-二-O-异亚丙基-3-C-（R，S）硝基（甲氧基-羰基）甲基-α-d-呋喃呋喃糖（2）。用钯/木炭还原乙酸硝基酯3得到肟4，而用阮内镍还原3乙酸酯得到甲基l（和d）-2-（3-O-乙酰基-1,2：5,6-di -O-异亚丙基-α-d-氟呋喃-3-基）-甘氨酸盐（5和6），分别以67％和8％的产率。5和6的皂化得到糖-3-基-α-氨基酸11和12。通过在炭载钯存在下用甲醇和乙酸酐处理2，将异呋喃并-3-基加合物2转化为葡糖呋喃-3-基还原产物13和14。N-三氟乙酰基衍生物（10）为5，经过66％的乙酸选择性水解，得到二醇，将其乙酰化，得到别乙酸三酯15。通过标准反应将5,6-乙二醇选择性降解，得到N-乙酰基-1--2-（5-O-乙酰基-1

  DOI：

  10.1016/s0008-6215(00)85132-0

文献信息

• Oxidation-reduction sequence for the synthesis of peracylated fluorodeoxy pentofuranosides
  作者：Igor A. Mikhailopulo、Grigorii G. Sivets、Nicolai E. Poopeiko、Natalia B. Khripach

  DOI：10.1016/0008-6215(95)00230-8

  日期：1995.11

  Abstract The oxidation of methyl 5-O- benzyl-3(2)-deoxy-3(2)-fluoro- α- d - pentofuranosides with dimethyl sulfoxide-acetic (trifluoroacetic) anhydride was accompanied by epimerization at the carbon atom bearing a fluoro function, resulting in the formation of the corresponding 2- or 3-keto derivatives as mixtures of two epimers in high combined yield. Reduction of a mixture of the erythro / threo

  摘要用二甲基亚砜-乙酸酐（三氟乙酸酐）氧化甲基5-O-苄基-3（2）-脱氧-3（2）-氟-α-d-戊呋喃糖苷的同时在带有氟的碳原子上发生差向异构化功能，导致形成相应的2-或3-酮衍生物，作为两种差向异构体的混合物，并具有很高的综合收率。在苯-乙醇中还原赤型/苏式差向异构体2-酮糖（以稳定水合物形式分离）与硼氢化钠的混合物进行立体选择性分离，分别导致3-脱氧-3-氟核糖和lyxo-呋喃糖苷的形成。在3-酮糖的核糖和阿拉伯糖差向异构体（被分离为游离酮）的情况下，对于2-脱氧-2-氟核糖，前者的还原立体选择性> 95％。3：对于后者，获得了1 lyxo /阿拉伯糖比例的产物。在室温下，用三乙胺在四氯化碳中处理2-异构体3-酮糖的混合物3-5小时，得到2-脱氧-2-氟核糖酮（约90％）。1-O-乙酰基-2,5-二-O-苯甲酰基-3-脱氧-3-氟-α，β-d-呋喃呋喃糖（8）和1-O-乙酰基-3,5
• Facile, highly stereoselective synthesis of 2′,3′-dideoxy- and 2′,3′-didehydro-2′,3t'-dideoxy nucleosides via a furanoid glycal intermediate
  作者：Choung Un Kim、Peter F. Misco

  DOI：10.1016/0040-4039(92)89018-8

  日期：1992.9

  Regiospecific and highly Stereoselective electrophilic addition reactions to the furanoid glycal 10 have been used as key steps in the synthesis of ddA and d4T antiviral nucleosides.

  对呋喃糖基糖醛10的区域特异性和高度立体选择性的亲电加成反应已被用作合成ddA和d4T抗病毒核苷的关键步骤。
• PROCESS FOR PRODUCING NUCLEOSIDE DERIVATIVE
  申请人：Japan Tobacco Inc.

  公开号：EP0598910A1

  公开（公告）日：1994-06-01

  A process for producing a nucleoside derivative (1) by reacting a substituted 2,3-dihydrofuran derivative (2) with an organohalogen compound (3) containing a group 16 element of the periodic table to give a substituted 2- halotetrahydrofuran derivative (4), condensing the derivative (4) with a nucleic acid base to give a substituted nucleoside derivative (5), and reducing the derivative (5), wherein R1 represents hydrogen, alkyl or R6-O-CH2-; R2 to R4 represent each hydrogen or a group containing a group 14-17 element of the periodic table; R5 represents optionally substituted alkyl or phenyl; A represents a group 16 element of the periodic table; B represents a nucleic acid base; and X represents halogen.

  通过将取代的2,3-二氢呋喃衍生物（2）与含周期表第16族元素的有机卤化物（3）反应，从而得到取代的2-卤代四氢呋喃衍生物（4），将衍生物（4）与核酸碱基缩合以得到取代的核苷衍生物（5），并还原衍生物（5），从而生产核苷衍生物（1）的方法，其中R1代表氢、烷基或R6-O-CH2-；R2到R4分别代表氢或含周期表第14-17族元素的基团；R5代表可选择地取代的烷基或苯基；A代表周期表第16族元素；B代表核酸碱基；X代表卤素。
• Total Synthesis of (+)-Sinefungin
  作者：Arun K. Ghosh、Wenming Liu

  DOI：10.1021/jo960670g

  日期：1996.1.1

  Sinefungin (1) a nucleoside antibiotic isolated from Streptomyces has been synthesized from D-ribose. Both the C-6 and C-9 stereogenic centers were constructed by efficient asymmetric syntheses. The C-6 amine stereochemistry was set by a highly diastereoselective allylation (>99% de) of a (1S,2R)-1-amino-2-indanol-derived oxazolidinone 9 followed by a Curtius rearrangement of 11 to 12. The C-9 amino

  Sinefungin（1）是从D-核糖合成的从链霉菌分离的核苷抗生素。C-6和C-9立体生成中心均通过有效的不对称合成构建。C-6胺的立体化学是通过（1S，2R）-1-氨基-2-茚满醇衍生的恶唑烷酮9的高度非对映选择性烯丙基化（> 99％de）进行的，然后Curtius重排为11至12。西诺芬净（-1）的-9个氨基酸立体化学是通过铑手性双膦催化α-（酰基氨基）丙烯酸酯衍生物的不对称氢化而建立的。发现在C-6氨基甲酸酯NH的存在下，异头乙酸酯20的混合物的异头腺苷化是非常困难的。在腺苷基化反应之前，必须将C-6氨基甲酸酯NH转化为其N-苄基衍生物21。
• Synthesis of Optically Active Nucleoside Analogs Containing 2,3-Dideoxyapiose in the Presence of a Catalytic Amount of Trimethylsilyl Iodide.
  作者：Keiko OHSAWA、Tatsushi SHIOZAWA、Kazuo ACHIWA、Yoshiyasu TERAO

  DOI：10.1248/cpb.41.1906

  日期：——

  Optically pure (R)-4, 4-diethoxy-2-(hydroxymethyl)butyl acetate (1) was synthesized enantioselectively by lipase-catalyzed transesterification from 4, 4-diethoxy-2-(hydroxymethyl)butanol. Coupling of silylated nucleobases and 2-O-acetyl-5-O-pivaloyl-(3S)-2, 3-dideoxyapiose (2) prepared from 1 was found to proceed smoothly in the presence of a catalytic amount of trimethylsilyl iodide under mild conditions to afford optically active nucleoside analogs.

  光学纯的(R)-4, 4-二乙氧基-2-(羟甲基)丁酸乙酯(1)是通过脂肪酶催化的酯交换反应，从4, 4-二乙氧基-2-(羟甲基)丁醇合成得到的。发现将硅化的核苷碱基与从1制备的2-O-乙酰基-5-O-匹伐酰基-(3S)-2, 3-脱氧阿葡萄糖(2)在温和条件下，在催化量的三甲基硅基碘化物存在下，可以顺利进行反应，生成光学活性的核苷类似物。