1-(2,3,5-tri-O-benzoyl-α-D-arabinofuranosyl)thymine | 80393-99-3

• 分子结构分类: 有机化合物 - 核苷、核苷酸和类似物 - 嘧啶核苷
• 英文名称: 1-(2,3,5-tri-O-benzoyl-α-D-arabinofuranosyl)thymine
• 英文别名: 1-(2,3,5-Tri-O-benzoyl-α-D-arabinofuranosyl)-5-methyluracil；1-(2',3',5'-Tri-O-benzoyl-alpha-D-arabinofuranosyl)thymine；[(2R,3R,4S,5S)-3,4-dibenzoyloxy-5-(5-methyl-2,4-dioxopyrimidin-1-yl)oxolan-2-yl]methyl benzoate
• CAS: 80393-99-3
• 化学式: C₃₁H₂₆N₂O₉
• 分子量: 570.555
• InChiKey: BJGXIHNHRIWKHA-QUUPDEESSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  42
• 可旋转键数：
  11
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  138
• 氢给体数：
  1
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  1-(2,3,5-tri-O-benzoyl-α-D-arabinofuranosyl)thymine 在 吡啶 、 4-二甲氨基吡啶 、 四丁基氟化铵 、 sodium methylate 、 溶剂黄146 作用下， 以 四氢呋喃 、 甲醇 、 二氯甲烷 为溶剂， 反应 76.75h， 生成 N4-[2-(4-nitrophenyl)ethoxycarbonyl]-1-{5-O-(4-monomethoxytrityl)-2-O-[2-(4-nitrophenyl)ethoxycarbonyl]-α-D-arabinofuranosyl}cytosine
  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：

  胸腺嘧啶 在 硫酸氢铵 、 N,O-双三甲硅基乙酰胺 作用下， 以 乙腈 为溶剂， 反应 3.5h， 生成 1-(2,3,5-tri-O-benzoyl-α-D-arabinofuranosyl)thymine
  参考文献：
  名称：

  在碘化钾包被的天然磷酸盐存在下，使用N，O-二甲基甲硅烷基乙酰胺方便地合成核苷的方法

  摘要：

  通过1-O-乙酰基D / L-阿拉伯糖和木呋喃糖的N-糖基化和甲硅烷基化的核碱基（尿嘧啶，胸腺嘧啶）在温和条件下以高收率合成了几种α-D/ L-阿拉伯糖苷和β-D/ L-木糖苷使用在BSA中用碘化钾包被的天然磷酸盐（NP）作为催化剂，在乙腈中加入6-氮杂尿嘧啶和6-氮杂嘧啶）。

  DOI：

  10.2174/157017810791112441

文献信息

• A Surprising Ring Opening Mechanism in the Formation of α-D-Arabinofuranosyl Nucleosides from 5-Substituted Uracils
  作者：Per Trolle Jørgensen、Erik B. Pedersen、Claus Nielsen

  DOI：10.1055/s-1992-26363

  日期：——

  Reaction of silylated 5-substituted uracil derivatives 6 with methyl 2,3,5-tri-O-benzoyl-α-D-arabinofuranoside (3) in the presence of trimethylsilyl trifluoromethanesulfonate afforded a mixture of the corresponding 5-substituted 1-(2,3,5-tri-O-benzoyl-α-D-arabinofuranosyl)uracils 7 and the acyclo 2,3,5-tri-O-benzoyl-1-O-methyl-1-(uracil-1-yl)-D-arabinitols 9 with the methoxy group intact at C-1. Compound 7 was deprotected with methanolic ammonia to give 8. Compound 7 was also reacted with Lawesson's Reagent to generate the corresponding 4-thio-α-D-arabinofuranoside nucleoside 14 which was deprotected by treatment with methanolic ammonia to give the nucleosides 15. Deprotected acyclo nucleosides 10 were likewise obtained from compounds 9. The mechanism for formation of the nucleosides 7 is discussed and the acyclo nucleosides 9 are believed to be intermediates.

  在三甲基硅基三氟甲磺酸酯的存在下，硅烷化的5-取代尿嘧啶衍生物6与甲基2,3,5-三-O-苯甲酰基-α-D-阿拉伯呋喃糖苷（3）反应，生成相应的5-取代1-(2,3,5-三-O-苯甲酰基-α-D-阿拉伯呋喃糖基)尿嘧啶7和非环状的2,3,5-三-O-苯甲酰基-1-O-甲基-1-(尿嘧啶-1-基)-D-阿拉伯醇9的混合物，其中C-1位的甲氧基保持完整。化合物7通过与甲醇氨反应去保护，得到8。化合物7还与Lawesson试剂反应，生成相应的4-硫-α-D-阿拉伯呋喃糖核苷14，后者通过甲醇氨处理去保护，得到核苷15。从化合物9也得到了去保护的非环状核苷10。讨论了核苷7的形成机理，并且认为非环状核苷9是中间体。
• Oligo (.alpha.-arabinofuranosyl nucleotides) and
  申请人：Microprobe Corporation

  公开号：US05177196A1

  公开（公告）日：1993-01-05

  Novel oligonucleotides formed from .alpha.-D-arabinofuranosyl nucleoside monomers, including oligonucleotides in which one or more of the monomer units is functionalized, are disclosed herein, as well as functionalized monomeric .alpha.-D-arabinofuranosyl nucleosides and nucleotides. A generic formula for the oligomers is: ##STR1## in which B is a nucleotide base which will vary from one monomeric unit to the next in a preselected oligonucleotide sequence; R is phosphate, phsophorothioate, phosphoramidate, or alkanephosphonate; t is 1 for functionalized monomeric units and zero for the others; W is a chemical linker arm; A is a functional group; and n is the number of monomeric units in the oligomer. The oligomers are useful for diagnostic and chemotherapeutic uses. A novel reaction is also disclosed, in which an .alpha.-D-arabinofuranosyl nucleoside with exposed hydroxyls at the 2'- and 3'-positions is selectively protected at the 2'-position in a single reaction.

  本文披露了由α-D-阿拉伯糖核苷单体形成的新型寡核苷酸，包括其中一个或多个单体单元被功能化的寡核苷酸，以及功能化单体α-D-阿拉伯糖核苷和核苷酸。 寡聚物的通用公式为：##STR1## 其中B是核苷酸碱基，将在预选的寡核苷酸序列中从一个单体单元到下一个单体单元变化; R是磷酸盐，磷硫酸盐，磷酰胺酯或脂肪族磷酸酯; t为1用于功能化单体单元，其他单体单元为零; W是化学连接臂; A是功能基团; n是寡聚物中单体单元的数量。 这些寡聚体可用于诊断和化疗用途。 还披露了一种新的反应，在该反应中，具有2'-和3'-位暴露羟基的α-D-阿拉伯糖核苷在单个反应中在2'-位置被选择性地保护。
• Propargyl 1,2-Orthoesters for a Catalytic and Stereoselective Synthesis of Pyrimidine Nucleosides
  作者：Boddu Venkateswara Rao、Sujit Manmode、Srinivas Hotha

  DOI：10.1021/jo502413z

  日期：2015.2.6

  Pyrimidine nucleosides are synthesized by using propargyl 1,2-orthoesters and Au(III) salt as a catalyst. Strategically positioned 1,2-orthoesters are found to yield only 1,2-trans nucleosides and enable preparation of 2'-OH containing pyrimidine nucleosides. The glycosyl donor employed in this study is stable and easily accessible. The identified high-yielding protocol is mild, diastereoselective, and catalytic.
• OLIGO(ALPHA-ARABINOFURANOSYL NUCLEOTIDES) AND ALPHA-ARABINOFURANOSYL PRECURSORS THEREOF
  申请人：MICROPROBE CORPORATION

  公开号：EP0543913A1

  公开（公告）日：1993-06-02
• EP0543913A4
  申请人：——

  公开号：EP0543913A4

  公开（公告）日：1995-10-04