6-formyl-5'-O-tert-butyldimethylsilyl-2',3'-O-isopropylideneuridine | 177779-23-6

• 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: 6-formyl-5'-O-tert-butyldimethylsilyl-2',3'-O-isopropylideneuridine
• 英文别名: 3-[(3aR,4R,6R,6aR)-6-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,2-dimethyl-3a,4,6,6a-tetrahydrofuro[3,4-d][1,3]dioxol-4-yl]-2,6-dioxopyrimidine-4-carbaldehyde
• CAS: 177779-23-6
• 化学式: C₁₉H₃₀N₂O₇Si
• 分子量: 426.542
• InChiKey: ZLDXIESXDMSONN-DTZQCDIJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.79
• 重原子数：
  29
• 可旋转键数：
  6
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.74
• 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：

  6-formyl-5'-O-tert-butyldimethylsilyl-2',3'-O-isopropylideneuridine 在 咪唑 、 三氟乙酸 作用下， 以 二氯甲烷 、 水 、 N,N-二甲基甲酰胺 为溶剂， 反应 3.5h， 生成 2',3',5'-tris-O-(tert-butyldimethylsilyl)-6-(2,2-dibromovinyl)uridine
  参考文献：
  名称：

  Cyclization Reactions of Nucleoside Anomeric Radical with Olefin Tethered on Base:  Factors That Induce Anomeric Stereochemistry

  摘要：

  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.

  DOI：

  10.1021/jo990611d
• 作为产物：
  描述：

  5'-O-(t-butyldimethylsilyl)-2',3'-O-isopropylideneuridine 在 selenium(IV) oxide 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 1,4-二氧六环 、 溶剂黄146 为溶剂， 反应 26.0h， 生成 6-formyl-5'-O-tert-butyldimethylsilyl-2',3'-O-isopropylideneuridine
  参考文献：
  名称：

  6-叠氮基和6-叠氮基甲基尿嘧啶核苷

  摘要：

  叠氮核苷已用于点击反应、代谢掺入细胞 DNA 以及活细胞的荧光成像。两类6-叠氮基修饰的尿嘧啶核苷；一瓦...

  DOI：

  10.1080/15257770.2023.2271023

文献信息

• Face selective 6,1′-(1-oxo)ethano bridge formation of uracil nucleosides under hypoiodite reaction conditions
  作者：Atsushi Kittaka、Hajime Kato、Hiromichi Tanaka、Yumiko Nonaka、Midori Amano、Kazuo T. Nakamura、Tadashi Miyasaka

  DOI：10.1016/s0040-4020(99)00232-x

  日期：1999.4

  Synthesis of novel spiro uracil nucleosides with an anomeric orthoester structure in a stereoselective manner under the hypoio dite reaction conditions of Heusler-Kalvoda and Suárez is fully described. While 2′-deoxy-6-(hydroxymethyl)uridine 2 and 2′-deoxy-6-[(1-hydroxy-1-methyl)ethyl]uridine 4 gave β- and α-spiro nucleosides in 43–68% yields with low selectivity (), the secondary ary alcohols 3a and

  充分描述了在Heusler-Kalvoda和Suárez的低碘反应条件下以立体选择性方式合成具有异头酯原酸酯结构的新型螺尿嘧啶核苷。2'-deoxy-6-（羟甲基）尿苷2和2'-deoxy-6-[（1-羟基-1-甲基）乙基]尿苷4以43-68％的产率得到β-和α-螺代核苷，由于低选择性（），仲醇3a和3b的化学产率为68–79％，选择性明显好于（）。在该6-（羟基）尿苷同行的方向6-8，16-17，和19似乎不仅受2'-取代基的控制，而且受C6-侧链的C7-立体中心的手性的控制，就像在2'-脱氧尿苷系列中一样。该反应的过渡态的几何形状被假定基于环化产物的X射线晶体结构20 α和24 β。
• Definitive Solution Structures for the 6-Formylated Versions of 1-(βD-Ribofuranosyl)-, 1-(2′-Deoxy-β-D-Ribofuranosyl)-, and 1-β-D-Arabinofuranosyluracil, and of Thymidine
  作者：Michael P. Groziak、Ronghui Lin、William C. Stevens、Linda L. Wotring、Leroy B. Townsend、J. Balzarini、M. Witvrouw、E. De Clercq

  DOI：10.1080/07328319608002033

  日期：1996.5

  ROESY and NOESY NMR spectroscopic analyses of the ribofuranosyl (la), 2'-deoxyribofuranosyl (Ib), and arabinofuranosyl (Ic) derivatives of 6-formyluracil in (CD3)(2)SO and D2O solutions have established that each exclusive 7,O5'-cyclic hemiacetal diastereomer of la,b and the major 7,O2'-cyclic hemiacetal diastereomer of Ic possess the 7R configuration. In addition, (7R)-1c has been shown to be thermodynamically more stable than (7S)-1c, contrary to our previous indication. A new, higher yielding synthetic route to in has been developed, Ib has been obtained for the first time in crystalline form, the route to Ic has been modified to better accommodate large scale preparations, and a new, fourth member of this class, 6-formylthymidine (Id), has been synthesized and its solution structures in (CD3)(2)SO, D2O, and CD3OD have been determined. Antitumor and antiviral evaluations of la-e have revealed no significant levels of activity.
• The 5′,6-Oxomethylene Transglycosidic Tether for Conformational Restriction of Pyrimidine Ribonucleosides. Investigation of 6-Formyl- and 6-(Hydroxymethyl)uridine 5′-Carboxaldehydes
  作者：Michael P. Groziak、Ronghui Lin

  DOI：10.1016/s0040-4020(00)00970-4

  日期：2000.12

  In an effort to develop a new motif for the transglycosidic tethering of the pyrimidine nucleoside framework, the 2',3'-O-isopropylidenated and unprotected versions of 6-formyl- and 6-(hydroxymethyl)uridine 5'-carboxaldehyde were prepared and these were examined for their ability to adopt 5',6-oxomethylene tethered solution structures. In aqueous solution, the 2',3'-O-isopropylidenated nucleosides readily generated spiro-dihydrouridines via proximity-induced transglycosidic intramolecular reactions. In stark contrast, their unprotected counterparts existed mainly as the untethered aldehyde hydrates. Based on these findings, the 5',6-oxomethylene transglycosidic tether appears to constitute a useful conformational restriction motif for the pyrimidine ribonucleoside flamework, but only when the 5'-OH group is functionalized. (C) 2000 Elsevier Science Ltd. All rights reserved.
• 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