1-[3,5-Bis-O-(1,1,3,3-tetraisopropyldisilox-1,3-diyl)-2-deoxy-β-D-erythro-furanosyl]uracil-6-carboxaldehyde | 149857-04-5

• 分子结构分类: 有机化合物 - 有机杂环化合物
• 英文名称: 1-[3,5-Bis-O-(1,1,3,3-tetraisopropyldisilox-1,3-diyl)-2-deoxy-β-D-erythro-furanosyl]uracil-6-carboxaldehyde
• 英文别名: 6-formyl-2'-deoxyuridine-3',5'-(1,1,3,3-tetraisopropyl)disiloxane；1-[2'-deoxy-3',5'-O-(tetraisopropyldisiloxane-1,3-diyl)-β-D-ribofuranosyl]uracil-6-carboxaldehyde；3-[(6aR,8R,9aS)-2,2,4,4-tetra(propan-2-yl)-6a,8,9,9a-tetrahydro-6H-furo[3,2-f][1,3,5,2,4]trioxadisilocin-8-yl]-2,6-dioxopyrimidine-4-carbaldehyde
• CAS: 149857-04-5
• 化学式: C₂₂H₃₈N₂O₇Si₂
• 分子量: 498.724
• InChiKey: FUGCQPGAYIUTAR-QKNQBKEWSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.59
• 重原子数：
  33
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.77
• 拓扑面积：
  103
• 氢给体数：
  1
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  1-[3,5-Bis-O-(1,1,3,3-tetraisopropyldisilox-1,3-diyl)-2-deoxy-β-D-erythro-furanosyl]uracil-6-carboxaldehyde 在 吡啶 、 lithium hydroxide 、 四丁基氟化铵 、 水 、 1-羟基苯并三唑 、 silver nitrate 、 盐酸-N-乙基-Nˊ-(3-二甲氨基丙基)碳二亚胺 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 、 苯 为溶剂， 反应 25.5h， 生成 (2E)-3-[3-(5-{[bis(4-methoxyphenyl)(phenyl)methoxy]methyl}-4-hydroxytetrahydrofuran-2-yl)-2,6-dioxo-1,2,3,6-tetrahydropyrimidin-4-yl]-N-[6-({[3-(4-nitrophenyl)-1-adamantyl]acetyl}amino)hexyl]acrylamide
  参考文献：
  名称：

  Hapten-phosphoramidites based on 6-[(2E)-N-(hexyl)prop-2-enamidyl]-2′-deoxyuridine

  摘要：

  Novel hapten-phosphoramidites 11a c were prepared from 2'-deoxyuridine (2) by functionalization at the 6-position and subsequent conjugation with adamantane, carbazole and dansyl reporter groups in good overall yield. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)01091-7
• 作为产物：
  描述：

  2-脱氧尿苷 在 六甲基磷酰三胺 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 N,N-二甲基甲酰胺 为溶剂， 生成 1-[3,5-Bis-O-(1,1,3,3-tetraisopropyldisilox-1,3-diyl)-2-deoxy-β-D-erythro-furanosyl]uracil-6-carboxaldehyde
  参考文献：
  名称：

  Hapten-phosphoramidites based on 6-[(2E)-N-(hexyl)prop-2-enamidyl]-2′-deoxyuridine

  摘要：

  Novel hapten-phosphoramidites 11a c were prepared from 2'-deoxyuridine (2) by functionalization at the 6-position and subsequent conjugation with adamantane, carbazole and dansyl reporter groups in good overall yield. (C) 2001 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4039(01)01091-7

文献信息

• Synthesis of hapten–phosphoramidites from 2′-deoxyuridine
  作者：Maciej Adamczyk、Srinivasa Rao Akireddy、Phillip G Mattingly、Rajarathnam E Reddy

  DOI：10.1016/s0040-4020(03)00875-5

  日期：2003.7

  A total of 11 novel phosphoramidites, 3a-d, 4a-d and 14a-c were prepared from 2'-deoxyuridine functionalized at 5 and 6-position of the pyrimidine ring with hapten reporter groups, e.g. adamantane, carbazole, dansyl and dabsyl, suitable for use in immunodetection nucleic acid testing assays. (C) 2003 Elsevier Science Ltd. All rights reserved.
• A new class of nucleosides possessing unusual physical properties: syntheses, hydration, and structural equilibria of 1-(.beta.-D-glycofuranosyl)uracil-6-carboxaldehydes
  作者：Michael P. Groziak、Ali Koohang、William C. Stevens、Paul D. Robinson

  DOI：10.1021/jo00067a044

  日期：1993.7

  The 1-beta-D-ribofruanosyl, 1-(2'-deoxy-beta-D-ribofuranosyl), and 1-beta-D-arabinofuranosyl derivatives (1a-c) of uracil-6-carboxaldehyde have been prepared for physicochemical analysis. The NMR-determined hydration and structural equilibria of 1a-c in both D2O and (CD3)2SO solution are compared, and the single-crystal X-ray structure of 1a is presented. Due to the high degree of electrophilic nature of their aldehyde moiety, all three nucleosides exhibit a strong ProclivitY toward existing as cyclic hemiacetal structures in solution; one such structure was found to be the sole constituent in the solid state for 1a. Using a [formyl-C-13]-labeled derivative of a synthetic precursor to 1a, the 1DELTAC-13(O-18) shielding isotope shift effects produced upon hydrate formation were determined at a +/- 1 ppb level, giving reference values of biomechanistic importance.
• Cyclization Reactions of Nucleoside Anomeric Radical with Olefin Tethered on Base:  Factors That Induce Anomeric Stereochemistry
  作者：Atsushi Kittaka、Takashi Asakura、Tetsuya Kuze、Hiromichi Tanaka、Naoki Yamada、Kazuo T. Nakamura、Tadashi Miyasaka

  DOI：10.1021/jo990611d

  日期：1999.9.1

  Nucleoside anomeric radicals were formed through 1,5-translocation of vinyl radicals generated from the 2,2-dibromovinyl group tethered at the uracil 6-position (1, 2, and 4) by tin radical. The anomeric radicals attacked the resulting C-6 vinyl group in a 5-endo-trig manner to afford anomeric spiro nucleosides (11-13, 21, 23, and 24) with the 6,1'-etheno bridge as the major cyclized products. The anomeric stereochemistry of the cyclization was found to be affected by the 2'-substituent. To consider the structure of the intermediate anomeric radical, the reaction using alpha-6-(2,2-dibromovinyl)-2'-deoxyuridine 9 was investigated. The same anomeric beta/alpha-stereoselectivity as the counterpart of 2 showed that the nucleoside anomeric radical would have nearly a planar structure and the C1'-N1. bond rotation in the radical is much faster than cyclization. The origin of the minor spiro nucleosides (14-20, 22, and 25-28) with the 6,1'-ethano bridge has also been investigated and appeared to be (E)-6-(2-bromovinyl)uridine 7E, a reduced form of 1a, but not (Z)-6-(2-bromovinyl)uridine 7Z, which gave a novel type of unstable compound with 6-exomethylene structure 29 through a different reaction pathway. 6-Chloro-8-(2,2-dibromovinyl)purine nucleoside 10 was next studied, and not only 1,5- but also 1,6-translocated products were isolated.
• 1,5-Translocation Strategy for Nucleoside Anomeric Radicals
  作者：Atsushi Kittaka、Hiromichi Tanaka、Naoki Yamada、Hajime Kato、Tadashi Miyasaka

  DOI：10.1080/07328319708006197

  日期：1997.7

  A new method for generating nucleoside anomeric radicals utilizing radical 1,5-translocation was developed. Two kinds of beta-halogenovinyl groups at the C6-position of uracil nucleosides were found to be a good radical source, which subsequently forms a nucleoside anomeric radical. The following 5-endo-trig cyclization gave anomeric spiro nucleosides as products.
• C-1′ Radical-Based Approaches for the Synthesis of Anomeric Spironucleosides
  作者：Chryssostomos Chatgilialoglu、Thanasis Gimisis、Gian Piero Spada

  DOI：10.1002/(sici)1521-3765(19991001)5:10<2866::aid-chem2866>3.0.co;2-6

  日期：1999.10.1