1-[3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-D-erythro-pento-1-enofuranosyl]uracil | 55264-13-6

• 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: 1-[3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-D-erythro-pento-1-enofuranosyl]uracil
• 英文别名: 1-<3,5-bis-O-(tert-butyldomethylsilyl)-2-deoxy-D-erythro-pent-1-enofuranosyl>uracil；1-<3,5-Bis-O-(tert-butyldimethylsilyl)-2-deoxy-D-erythro-pent-1-enofuranosyl>uracil；1-[O³,O⁵-bis-(tert-butyl-dimethyl-silanyl)-D-erythro-2-deoxy-pent-1-enofuranosyl]-1H-pyrimidine-2,4-dione；1-[(2R,3S)-3-[tert-butyl(dimethyl)silyl]oxy-2-[[tert-butyl(dimethyl)silyl]oxymethyl]-2,3-dihydrofuran-5-yl]pyrimidine-2,4-dione
• CAS: 55264-13-6
• 化学式: C₂₁H₃₈N₂O₅Si₂
• 分子量: 454.714
• InChiKey: YHZNBGDOFMKYAH-JKSUJKDBSA-N

物化性质

• 密度：
  1.07±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.15
• 重原子数：
  30
• 可旋转键数：
  8
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  77.1
• 氢给体数：
  1
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  1-[3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-D-erythro-pento-1-enofuranosyl]uracil 在 甲醇 、 ammonium cerium(IV) nitrate 、 silica gel 作用下， 生成 (5S)-5-(tert-butyldimethylsilanyloxymethyl)-5H-furan-2-one
  参考文献：
  名称：

  不饱和核苷的催化重排重排

  摘要：

  尝试向1'，2'-不饱和核苷分子间添加丙二酰基自由基导致了呋喃酮的意外形成。因此，只有催化量的硝酸铈（IV）铵（CAN）会引起费勒重排。分离的不饱和内酯收率很高，可以用作合成光学活性产物的前体。

  DOI：

  10.1016/s0040-4039(98)02264-3
• 作为产物：
  描述：

  (2R,3R,3aS,9aR)-3-((tert-butyldimethylsilyl)oxy)-2-(((tert-butyldimethylsilyl)oxy)methyl)-3,3a-dihydro-2H-furo[2',3':4,5]oxazolo[3,2-a]pyrimidin-6(9aH)-one 在 lithium aluminium tetrahydride 、 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 29.17h， 生成 1-[3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-D-erythro-pento-1-enofuranosyl]uracil
  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
• Ring Opening of Nucleoside 1‘,2‘-Epoxides with Organoaluminum Reagents:  Stereoselective Entry to Ribonucleosides Branched at the Anomeric Position
  作者：Kazuhiro Haraguchi、Yutaka Kubota、Hiromichi Tanaka

  DOI：10.1021/jo030262u

  日期：2004.3.1

  uridine (11) with dimethyldioxirane proceeded from the α-face to give the 1‘,2‘-α-epoxide 12. Upon reacting with organoaluminum reagents, the 1‘,2‘-α-epoxide 12 underwent preferential syn-opening of the epoxide ring to yield the β-anomers of 1‘-methyl- (13β), 1‘-ethyl- (14β), 1‘-isobutyl- (15β), 1‘-ethynyl- (16β), 1‘-vinyl- (17β), and 1‘-phenyl- (18β) uridine derivatives, although the corresponding α-anomers

  从α面开始用二甲基二环氧乙烷将3'，5'- O-（二叔丁基亚甲硅烷基）-1'，2'-不饱和尿苷（11）环氧化，得到1'，2'-α-环氧化合物12。在与有机铝试剂反应，1' ，2'-α环氧化物12后行优先顺式开口环氧化物环中以得到1'-甲基- （的β端基异构体13 β），1'-乙基- （14 β），1'-异丁基- （15 β），1'-乙炔基（16 β），1,1'-乙烯基- （17 β）和1'-苯基- （18 β）尿苷衍生物，尽管除了与三苯基铝反应以外，还形成了相应的α-端基异构体。然而，发现用苄氧甲基或苯甲酰基保护11的N 3-位可导致所需β-端基异构体的排他性形成。提出了可能的解释所观察到的立体化学结果。发现类似的策略适用于1'-支链腺苷类似物的合成，其中包括受保护的阿古霉素C（37）。
• An Intramolecular Anionic Migration of a Stannyl Group from the 6-Position of 1-(2-Deoxy- d - erythro -pent-1-enofuranosyl)uracil to the 2′-Position: Synthesis of 2′-Substituted 1′,2′-Unsaturated Uridines
  作者：Hiroki Kumamoto、Satoru Shindoh、Hiromichi Tanaka、Yoshiharu Itoh、Kazuhiro Haraguchi、Eisen Gen、Atsushi Kittaka、Tadashi Miyasaka、Masato Kondo、Kazuo T Nakamura

  DOI：10.1016/s0040-4020(00)00441-5

  日期：2000.7

  Lithiation of 1-[3,5-bis-O-(tert-butyldimethylsilyl)-2-deoxy-d-erythro-pent-1-enofuranosyl)uracil (1) takes place exclusively at the 6-position of the uracil base. The 6-tributylstannyl (or 6-trimethylsilyl) derivative prepared by quenching the C6-lithiated species with Bu3SnCl (or Me3SiCl) was found to undergo an intramolecular anionic migration to the 2′-positon of the furanoid glycal portion. By

  1- [3,5-双-O-（叔丁基二甲基甲硅烷基）-2-脱氧-二赤-戊-1-烯呋喃糖基）尿嘧啶（1）的锂化仅在尿嘧啶碱基的6-位发生。发现通过用Bu 3 SnCl（或Me 3 SiCl）淬灭C6-锂化的物质而制备的6-三丁基锡烷基（或6-三甲基甲硅烷基）衍生物发生分子内阴离子迁移至呋喃糖基糖部分的2'-正电子。通过操纵2'-锡烷基，首次制备了2'-卤素和2'-碳取代的1'，2'-不饱和尿苷。与报告的1的不稳定性相反在脱保护过程中，本研究中合成的2'-取代类似物经过NH 4 F的MeOH处理后，均一地以高收率均匀地提供了相应的游离核苷。
• 5-<i>Exo</i> versus 6-<i>Endo</i> Cyclization of Nucleoside 2-Sila-5-hexenyl Radicals:  Reaction of 6-(Bromomethyl)dimethylsilyl 1‘,2‘-Unsaturated Uridines
  作者：Junko Ogamino、Hideaki Mizunuma、Hiroki Kumamoto、Shingo Takeda、Kazuhiro Haraguchi、Kazuo T. Nakamura、Hiroshi Sugiyama、Hiromichi Tanaka

  DOI：10.1021/jo040260p

  日期：2005.3.1

  The mode of cyclization of 2-sila-5-hexen-1-yl radicals generated from 6-(bromomethyl)dimethylsilyl-1‘,2‘-unsaturated uridines was investigated. In contrast to the case of the 2‘-unsubstituted 6-silicon-tethered substrate (4), which undergoes exclusive 6-endo-cyclization, reactions of the 2‘-substituted (Me, CO2Me, OBz, and Cl) derivatives (14, 20, 22, and 24) uniformly proceeded in preferential or

  研究了由6-（溴甲基）二甲基甲硅烷基-1'，2'-不饱和尿苷生成的2-sila-5-hexen-1-yl自由基的环化模式。与此相反的2'-取代的6- -硅-拴系的底物（的情况4），其经历独家6-内切-cyclization，2'-取代的（Me中，CO的反应2 Me中，OBZ和Cl）衍生物（14，20，22，和24）中优先或独家5-均匀地进行外切-mode。还对所得环化产物进行了Tamoo氧化，以合成相应的1'- C-羟甲基衍生物。
• 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.