1-[5-(tert-Butyl-dimethyl-silanyloxymethyl)-furan-2-yl]-1H-pyrimidine-2,4-dione | 135824-42-9

• 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: 1-[5-(tert-Butyl-dimethyl-silanyloxymethyl)-furan-2-yl]-1H-pyrimidine-2,4-dione
• 英文别名: 1-[5-[[Tert-butyl(dimethyl)silyl]oxymethyl]furan-2-yl]pyrimidine-2,4-dione
• CAS: 135824-42-9
• 化学式: C₁₅H₂₂N₂O₄Si
• 分子量: 322.436
• InChiKey: KZWHJMNOVQIUCR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.64
• 重原子数：
  22
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  71.8
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  5’-O-三苯甲基尿苷-2’,3’-来苏-环氧化物 在 吡啶 、 sodium tetrahydroborate 、 溶剂黄146 、 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 4.17h， 生成 1-[5-(tert-Butyl-dimethyl-silanyloxymethyl)-furan-2-yl]-1H-pyrimidine-2,4-dione
  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

文献信息

• An alternative method for the synthesis of 2′-halogeno-1′,2′-unsaturated uridine derivatives through <i>syn</i>-elimination of pivalic acid of 2′-halogeno- 2′-deoxy-1′-pivaloyloxyuracil nucleoside: preparation of its 2′-<i>C</i>-branched nucleosides
  作者：Kazuhiro Haraguchi、Eisen Gen、Hiroki Kumamoto、Yoshiharu Itoh、Hiromichi Tanaka

  DOI：10.1080/15257770.2019.1641724

  日期：2020.2.20

  Abstract An alternative method for the preparation of 2′-bromo- (5b) and 2′-iodo- (5c) 1′,2′-unsaturated uracil nucleosides has been developed. The protocol was on the basis of the syn-elimination of pivalic acid from 2′-bromo-(7a,b) and 2′-iodo-(9a,b) 1′-pivaloyloxy-2′-deoxyuridine derivatives, which were derived from the halo-pivaloyloxylation of 3′,5′-bis-O-TBDMS-1′,2′-unsaturated uridine 1. Compounds

  摘要 已开发出一种制备 2'-溴-(5b) 和 2'-碘-(5c) 1',2'-不饱和尿嘧啶核苷的替代方法。该方案基于从 2'-溴-(7a,b) 和 2'-碘-(9a,b) 1'-新戊酰氧基-2'-脱氧尿苷衍生物中同步消除新戊酸，这些衍生物衍生来自 3',5'-双-O-TBDMS-1',2'-不饱和尿苷 1 的卤代新戊酰氧基化。 化合物 5b 和 5c 被证明可作为相应的 2'-C-支链 1' 的通用合成子,2'-不饱和尿嘧啶核苷，通过钯催化的交叉偶联或卤素-锂交换反应。图形概要
• Nucleophilic Addition of Benzenethiol to 1‘,2‘-Unsaturated Nucleosides:  1‘-<i>C</i>-Phenylthio-2‘-deoxynucleosides as Anomeric Radical Precursors
  作者：Hiroki Kumamoto、Miki Murasaki、Kazuhiro Haraguchi、Aki Anamura、Hiromichi Tanaka

  DOI：10.1021/jo0201934

  日期：2002.8.1

  The addition reaction of benzenethiol to the glycal portion of 1',2'-unsaturated uridine proceeds efficiently in the presence of Et3N. The mechanism involves nucleophilic attack of thiolate at the anomeric position in the rate-determining step, wherein conjugation between the nucleobase and the glycal portion is crucial. The derivative having a methyl group either at the 2'- or 6-position did not undergo this addition reaction, due to their sterically prohibited coplanarity. The 1',2'-unsaturated derivatives of thymine and adenine can also be used as substrates for this addition reaction. It was also shown that the resulting 1'-C-phenylthio-2'-deoxynucleosides serve as precursors for radical-mediated C-C bond formation at the anomeric position.
• Divergent and Stereocontrolled Approach to the Synthesis of Uracil Nucleosides Branched at the Anomeric Position
  作者：Yoshiharu Itoh、Kazuhiro Haraguchi、Hiromichi Tanaka、Eisen Gen、Tadashi Miyasaka

  DOI：10.1021/jo00108a031

  日期：1995.2

  Electrophilic addition of NBS/pivalic acid (bromopivaloyloxylation) to 1-[3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-D-erythro-pent- 1-enofuranosyl]uracil (2), readily accessible from O-2,2'-anhydro-uridine, furnished 1-[2-bromo-3,5-bis-O-(tert-butyldimethyylsilyl)-2-deoxy-1-(pivaloyloxy)-beta-D-ara-binofuranosyl]uracil (7) stereoselectively. This compound (7), having a leaving group at the 1'-position as well as 2'-beta-Br that could exert anchimeric assistance, serves as versatile intermediate for the stereocontrolled synthesis of various types of 1'-C-branched derivatives through nucleophilic substitutions by the use of organosilicon and organoaluminum reagents. The whole sequence constitutes the first example of the conversion of a naturally-occurring nucleoside to the analogues branched at the anomeric position.
• Anomeric manipulation of nucleosides: Stereosepecific entry to 1′-C-branched uracil nucleosides
  作者：Kazuhiro Haraguchi、Yoshiharu Itoh、Hiromichi Tanaka、Kentaro Yamaguchi、Tadashi Miyasaka

  DOI：10.1016/s0040-4039(00)91829-x

  日期：1993.10

  Uracil nucleosides variously branched at die anomeric position have been synthesized through stereoselective bromo-pivaloyloxylation of a 1',2'-unsaturated derivative and successive SnCl4-promoted nucleophilic substitution with organosilicon reagents. This constitutes the first example of C-C bond formation at the anomeric position of nucleoside.
• Stereoselective synthesis of 4′-C-branched 2,′3′-didehydro-2′-dideoxy nucleosides based on SnCl4-promoted allylic rearrangement
  作者：Kazuhiro Haraguchi、Hiromichi Tanaka、Yoshiharu Itoh、Shigeru Saito、Tadashi Miyasaka

  DOI：10.1016/s0040-4039(00)78874-5

  日期：1992.5

  Based on SnCl4-promoted allylic rearrangement between a 3',4'-unsaturated uracil nucleoside and organosilicon reagents, stereoselective introduction of carbon functionalities to the 4'-position has been accomplished, disclosing a new entry for a series of 4'-C-branched nucleosides of biological interests.