1-((2R,5S)-5-(((tert-butyldiphenylsilyl)oxy)methyl)tetrahydrofuran-2-yl)-5-methylpyrimidine-2,4(1H,3H)-dione | 121687-74-9

• 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-((2R,5S)-5-(((tert-butyldiphenylsilyl)oxy)methyl)tetrahydrofuran-2-yl)-5-methylpyrimidine-2,4(1H,3H)-dione
• 英文别名: 1-<5-O-(tert-butyldiphenylsilyl)-2,3-dideoxy-β-D-glycero-pentofuranosyl>thymine；1-[5-O-(tert-butyldiphenylsilyl)-2,3-dideoxy-β-D-erythro-pentofuranosyl]thymine；5'-O-tert-Butyldiphenylsilyl-3'-deoxythymidine；1-[5-O-(t-butyldiphenylsilyl)-2,3-dideoxy-β-D-glycero-pentofuranosyl]thymine；5'-O-(t-butyldiphenylsilyl)-3'-deoxythymidine；1-[(2R,5S)-5-[[tert-butyl(diphenyl)silyl]oxymethyl]oxolan-2-yl]-5-methylpyrimidine-2,4-dione
• CAS: 121687-74-9
• 化学式: C₂₆H₃₂N₂O₄Si
• 分子量: 464.637
• InChiKey: CHWVRXDEBUOTGE-NZQKXSOJSA-N

物化性质

• 熔点：
  150-152 °C
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.1
• 重原子数：
  33
• 可旋转键数：
  7
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.38
• 拓扑面积：
  67.9
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  1-((2R,5S)-5-(((tert-butyldiphenylsilyl)oxy)methyl)tetrahydrofuran-2-yl)-5-methylpyrimidine-2,4(1H,3H)-dione 在 四丁基氟化铵 作用下， 以 四氢呋喃 为溶剂， 反应 3.0h， 以80%的产率得到2',3'-二脱氧胸苷
  参考文献：
  名称：

  A highly stereoselective synthesis of anti-HIV 2',3'-dideoxy- and 2',3'-didehydro-2',3'-dideoxynucleosides

  摘要：

  A general total synthetic method for the stereocontrolled synthesis of 2',3'-dideoxy- as well as 2',3'-didehydro-2',3'-dideoxynucleosides is presented. Introduction of an alpha-phenylselenenyl group at the 2-position of 2,3-dideoxyribosyl acetate directs the glycosyl bond formation to give greater-than-or-equal-to 95% beta-isomer. This 2'-phenylselenenyl nucleoside may be converted to either the 2',3'-dideoxynucleoside by treatment with n-Bu3SnH and Et3B at room temperature or to the unsaturated derivative by treatment with H2O2/cat. pyridine. The application of this method to the syntheses of pyrimidines (ddU, ddT, ddC), 6-substituted purines (ddA, ddI, 6-chloro-ddP, N6-Me-ddA), and 2,6-disubstituted purines (2-F-ddA, 6-chloro-2-amino-ddP) as well as selected 2',3'-didehydro-2',3'-dideoxy derivatives is reported.

  DOI：

  10.1021/jo00040a031
• 作为产物：
  描述：

  beta-胸苷 在 吡啶 、 4-二甲氨基吡啶 、 N-羟基丁二酰亚胺 、 偶氮二异丁腈 作用下， 以 吡啶 、 苯 为溶剂， 反应 82.0h， 生成 1-((2R,5S)-5-(((tert-butyldiphenylsilyl)oxy)methyl)tetrahydrofuran-2-yl)-5-methylpyrimidine-2,4(1H,3H)-dione
  参考文献：
  名称：

  Efficient and Stereoselective Synthesis of 3′-Deoxy 3′ -C-Branched-Chain Substituted Thymidine

  摘要：

  在本报告中，我们首次利用分子间自由基 C-C 键形成反应，简便、高效、立体选择性地合成了 1-[5-O-(叔丁基二苯基硅烷基)-2,3-二脱氧-3-C-甲酰基-δ²-D-赤式戊呋喃糖基]胸腺嘧啶（12）。讨论了这种化合物在反义应用中的效用，作为延伸，12 被转化为 1-[2,3-二脱氧-3-C-(羟甲基)-δ-D-赤式戊呋喃糖基]胸腺嘧啶（14），这是一种有效的抗病毒和抗肿瘤药物。

  DOI：

  10.1055/s-1994-25664

文献信息

• Synthesis and evaluation of a series of 1-(3-alkyl-2,3-dideoxy-α,β-d-erythro-pentofuranosyl)thymines
  作者：Kwasi Agyei-Aye、David C. Baker

  DOI：10.1016/0008-6215(88)84079-5

  日期：1988.12

  A series of 1-(3-alkyl-2,3-dideoxy-alpha,beta-D-erythro-pentofuranosyl)thymines (3'-alkyl-3'-deoxythymidines) has been prepared from 5-O-(tert-butyldiphenylsilyl)-2,3-dideoxy-D-glycero-pent-2- enono-1,4-lactone ((S)-5-[(tert-butyldiphenylsilyl)oxymethyl]-2(5H)- furanone) by Michael addition of the appropriate organocopper reagent, followed by reduction of the lactone, acetylation of the resulting hemiacetal

  由5-O-（叔丁基二苯基甲硅烷基）制备了一系列1-（3-烷基-2,3-二脱氧-α，β-D-赤型-呋喃呋喃糖基）胸腺嘧啶（3'-烷基-3'-脱氧胸苷） ）-2,3-二脱氧-D-甘油-2-烯诺-1,4-内酯（（S）-5-[（叔丁基二苯基甲硅烷基）氧基甲基] -2（5H）-呋喃酮）适当的有机铜试剂，然后还原内酯，使所得的半缩醛乙酰化，并用三氟甲磺酸三甲基甲硅烷基酯催化与2，4-二-O-（三甲基甲硅烷基）胸腺嘧啶偶联。通过使用氟化四丁基铵使被保护的核苷脱甲硅烷基化，得到游离核苷的端基异构体混合物。类似地，由5-O-（叔丁基二苯基甲硅烷基）-2，3-二脱氧-D-甘油-戊烯-1制备未取代的2'，3'-二脱氧核苷类似物。
• Organocatalytic Conversion of Nucleosides to Furanoid Glycals
  作者：Edna Mao、Cheol K. Chung、Yining Ji、Yu-hong Lam、Peter E. Maligres

  DOI：10.1021/acs.joc.1c00555

  日期：2021.6.4

  2′-deoxynucleosides to furanoid glycals have been discovered. These phosphorimides, (Ph2PS)2NH and (Ph2PSe)2NH, were shown to effectively mediate persilylation of 2′-deoxynucleosides allowing the elimination of the nucleobase giving the corresponding glycal. These mild conditions were demonstrated in the syntheses of glycals with various substitution patterns while minimizing the formation of undesired byproducts

  已经发现了一类对将 2'-脱氧核苷转化为呋喃糖苷具有高活性的有机催化剂。这些磷酰亚胺(Ph 2 PS) 2 NH 和 (Ph 2 PSe) 2 NH 显示出可有效介导 2'-脱氧核苷的全甲硅烷基化，从而消除核碱基，产生相应的糖基。这些温和的条件在具有各种取代模式的糖醛的合成中得到了证明，同时最大限度地减少了不需要的副产物的形成并扩大了该方法的范围。
• Method for preparing 2'-3'-dideoxy-.beta.-nucleosides using
  申请人：Japan Tobacco, Incorporated

  公开号：US05416204A1

  公开（公告）日：1995-05-16

  2,3-Dideoxy-2,2-di(organothio)-B-D-pentofuranosyl-pyrimidines are disclosed as intermediates in the synthesis of 2', 3'-dideoxynucleosides and have the structure shown below. ##STR1## wherein R.sup.4 is a hydroxyl protecting group; X is oxygen or nitrogen, said nitrogen being bonded to a hydrogen atom, an alkyl or acyl group; Y is hydrogen, halogen, alkyl, haloalkyl or haloalkenyl; and R.sup.5 is alkyl, aralkyl, or aryl wherein aralkkyl or aryl is substituted with hydrogen, halogen, nitro or alkoxy. 2', 3'-Dideoxynucleosides, products of the above intermediates, are useful as antiviral agents.

  2,3-二去氧-2,2-二(有机硫)-B-D-戊呋喃核苷嘧啶是合成2',3'-二去氧核苷的中间体，具有以下结构。其中R^4是羟基保护基；X是氧或氮，所述氮与氢原子、烷基或酰基结合；Y是氢、卤素、烷基、卤代烷基或卤代烯基；R^5是烷基、芳基烷基或芳基，其中芳基烷基或芳基被氢、卤素、硝基或烷氧基取代。上述中间体的产物2',3'-二去氧核苷可用作抗病毒剂。
• SYNTHESIS AND PHOTOCHEMICAL BEHAVIOUR OF A T-T DIMER CONTAINING AN AMIDE LINKAGE
  作者：Martial Thomas、Pascale Clivio、Dominique Guillaume、Jean-Louis Fourrey

  DOI：10.1081/ncn-100002460

  日期：2001.3.31

  A T-T dimer characterized by an amide linkage to replace the phosphodiester backbone has been synthesized using a modified radical strategy. The new synthetic approach makes use of a thymidin-3'-yl phosphorodithioate derivative as a precursor of 3'-allyl-3'-deoxythymidine. Standard chemical transformations of this derivative led to the desired T-T dimer incorporating an amide bond. The latter was irradiated

  已使用改良的自由基策略合成了以酰胺键取代磷酸二酯主链为特征的TT二聚体。新的合成方法利用胸苷3'-基二硫代磷酸酯衍生物作为3'-烯丙基-3'-脱氧胸苷的前体。该衍生物的标准化学转化导致所需的掺入酰胺键的TT二聚体。后者用254 nm波长的光照射，主要生成环丁烷和[6-4]光加合物。
• Stereoselective glycosylation of hetercyclic bases
  申请人：University of Georgia Research Foundation, Inc.

  公开号：US05175267A1

  公开（公告）日：1992-12-29

  A method of preparation of 2',3'-dideoxy and 2',3'-dideoxy-2',3'-didehydronucleosides that includes the step of condensing a 1-O-activated-2-(aromatic or aliphatic)-selenenyl-5-O-protected ribose with a protected heterocyclic base in the presence of trimethylsilyl triflate or a Lewis acid to form a .beta.-anomeric nucleoside in high yield.

  一种制备2'，3'-去氧核苷和2'，3'-去氧-2'，3'-双脱氢核苷的方法，其中包括将1-O-活化的2-(芳香族或脂肪族)-硒基-5-O-保护核糖与保护的杂环碱在三甲基硅基三氟甲烷或路易斯酸存在下缩合，以高收率形成β-异构核苷。