(3R,5S,6S)-3-Phenyl-1,4-dioxa-7-thia-dispiro[4.0.4.3]tridec-9-en-2-one | 630059-93-7

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (3R,5S,6S)-3-Phenyl-1,4-dioxa-7-thia-dispiro[4.0.4.3]tridec-9-en-2-one
• 英文别名: (5S,6S,9R)-9-phenyl-7,10-dioxa-4-thiadispiro[4.0.46.35]tridec-1-en-8-one
• CAS: 630059-93-7
• 化学式: C₁₆H₁₆O₃S
• 分子量: 288.367
• InChiKey: DWBHVXVQHHISGI-KBMXLJTQSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  20
• 可旋转键数：
  1
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.44
• 拓扑面积：
  60.8
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (3R,5S,6S)-3-Phenyl-1,4-dioxa-7-thia-dispiro[4.0.4.3]tridec-9-en-2-one 在 三乙烯二胺 、 potassium dioxotetrahydroxoosmate(VI) 2,4,6-三甲基吡啶 、 六甲基磷酰三胺 、 lithium hydroxide 、 甲基磺酰胺 、 叔丁基锂 、 silver trifluoromethanesulfonate 、 aluminum isopropoxide 、 potassium carbonate 、 对甲苯磺酸 、 potassium hexacyanoferrate(III) 作用下， 以 四氢呋喃 、 水 、 N,N-二甲基甲酰胺 、 异丙醇 、 叔丁醇 、 正戊烷 为溶剂， 反应 34.0h， 生成 (1R,5S,11R)-7,7,9,9-Tetraisopropyl-6,8,10-trioxa-2-thia-7,9-disila-tricyclo[9.3.0.01,5]tetradec-3-ene
  参考文献：
  名称：

  Stereoselective Synthesis of Conformationally Constrained 2‘-Deoxy-4‘-thia β-Anomeric Spirocyclic Nucleosides Featuring Either Hydroxyl Configuration at C5‘

  摘要：

  An enantioselective approach to 2'-deoxy-4'-thia spirocyclic nucleosides featuring an alpha- or beta-hydroxyl substituent at C-5' of the carbocyclic ring is detailed. The starting point is the mandelate acetal 8. The overall strategy involves the stereocontrolled dihydroxylation of this dihydrothiophene, subsequent generation of the keto acetonide 12 followed by its Meerwein-Ponndorf-Verley reduction and beta-elimination, protection of the resulting dihydroxy thiaglycal, electrophilic glycosidation according to the Haraguchi protocol, reductive removal of the phenylseleno group, and end-game global deprotection. Acquisition of the alpha- and beta-5'-isomers is equally facile. Various ID and 2D NMR techniques are used for assigning configuration.

  DOI：

  10.1021/jo048071u
• 作为产物：
  描述：

  (4R,5R)-4-Phenylselanyl-1-thia-spiro[4.4]nonan-6-one 在 间氯过氧苯甲酸 、 scandium tris(trifluoromethanesulfonate) 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 50.67h， 生成 (3R,5S,6S)-3-Phenyl-1,4-dioxa-7-thia-dispiro[4.0.4.3]tridec-9-en-2-one
  参考文献：
  名称：

  具有在顶点位置结合的硫的C4′-螺烷基化的核苷。

  摘要：

  已经开发了基于硫鎓离子引发的羽状环扩环概念的方法学，用于获得C4'-螺环硫代核苷。容易获得的外消旋酮6和37通过缩醛与（R）-扁桃酸方便地拆分。利用Pummerer重排开始的后续反应使它们自身可以螺旋环核心的功能化，并最终掺入了核苷碱基。指出了该策略的局限性。同样容易获得在C4'的α-和β-异构体。通过X射线晶体学可以实现绝对的构型分配。

  DOI：

  10.1021/jo030196w

文献信息

• Spirocyclic Restriction of Nucleosides
  作者：Leo A. Paquette

  DOI：10.1071/ch03267

  日期：——

  The concept of spirocyclic restriction as applied broadly to the field of nucleoside mimics makes possible the generation of diastereomeric pairs configured with a syn- or anti-oriented hydroxyl substituent at C5′. The development of concise synthetic routes to spiro-fused nucleosides bearing all possible natural bases and expectedly capable of enforcing a conformation favourable for duplex formation on incorporation into oligomers represents a significant new direction in the design of antisense molecules. The present overview describes the convenient approaches that have been developed in this laboratory for accessing varied members of this class, including analogues that feature sulfur and carbon at the apical position.

  将螺环限制的概念广泛应用于核苷模拟物领域，可以生成在 C5′处配置有同步或反方向羟基取代基的非对映异构对。开发带有所有可能天然碱基的螺状融合核苷的简明合成路线，预计能在加入低聚物时形成有利于双链形成的构象，是设计反义分子的一个重要新方向。本综述介绍了本实验室为获得该类核苷的各种成员而开发的便捷方法，包括在顶端位置具有硫和碳的类似物。
• C4‘-Spiroalkylated Nucleosides Having Sulfur Incorporated at the Apex Position
  作者：Leo A. Paquette、Fabrizio Fabris、Fabrice Gallou、Shuzhi Dong

  DOI：10.1021/jo030196w

  日期：2003.10.1

  Methodology based on the concept of thionium ion-initiated pinacolic ring expansion has been developed for accessing C4'-spirocyclic thionucleosides. The readily available racemic ketones 6 and 37 are conveniently resolved via their acetals with (R)-mandelic acid. Subsequent reactions beginning with utilization of the Pummerer rearrangement lend themselves to functionalization of the spirocyclic core

  已经开发了基于硫鎓离子引发的羽状环扩环概念的方法学，用于获得C4'-螺环硫代核苷。容易获得的外消旋酮6和37通过缩醛与（R）-扁桃酸方便地拆分。利用Pummerer重排开始的后续反应使它们自身可以螺旋环核心的功能化，并最终掺入了核苷碱基。指出了该策略的局限性。同样容易获得在C4'的α-和β-异构体。通过X射线晶体学可以实现绝对的构型分配。
• Stereoselective Synthesis of Conformationally Constrained 2‘-Deoxy-4‘-thia β-Anomeric Spirocyclic Nucleosides Featuring Either Hydroxyl Configuration at C5‘
  作者：Shuzhi Dong、Leo A. Paquette

  DOI：10.1021/jo048071u

  日期：2005.3.1

  An enantioselective approach to 2'-deoxy-4'-thia spirocyclic nucleosides featuring an alpha- or beta-hydroxyl substituent at C-5' of the carbocyclic ring is detailed. The starting point is the mandelate acetal 8. The overall strategy involves the stereocontrolled dihydroxylation of this dihydrothiophene, subsequent generation of the keto acetonide 12 followed by its Meerwein-Ponndorf-Verley reduction and beta-elimination, protection of the resulting dihydroxy thiaglycal, electrophilic glycosidation according to the Haraguchi protocol, reductive removal of the phenylseleno group, and end-game global deprotection. Acquisition of the alpha- and beta-5'-isomers is equally facile. Various ID and 2D NMR techniques are used for assigning configuration.