1-硫杂螺[4.4]壬烷-6-酮 | 154470-63-0

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 硫杂环戊烷
• 中文名称: 1-硫杂螺[4.4]壬烷-6-酮
• 英文名称: 1-thiaspiro<4.5>decan-6-one
• 英文别名: 1-Thiaspiro[4.4]nonan-6-one；1-thiaspiro[4.4]nonan-9-one
• CAS: 154470-63-0
• 化学式: C₈H₁₂OS
• 分子量: 156.249
• InChiKey: RUQAFNPMUNFINH-UHFFFAOYSA-N

物化性质

• 沸点：
  266.1±13.0 °C(Predicted)
• 密度：
  1.15±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  10
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.88
• 拓扑面积：
  42.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  1-硫杂螺[4.4]壬烷-6-酮 在 lithium hydroxide 、 lithium aluminium tetrahydride 、 scandium tris(trifluoromethanesulfonate) 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 、 水 、 乙腈 为溶剂， 反应 80.0h， 生成 (5S,6R)-1-Thia-spiro[4.4]nonan-6-ol
  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
• 作为产物：
  描述：

  1-(2,3-Dihydrothiophen-5-yl)cyclobutan-1-ol 在 Dowex-50X resin 作用下， 以 二氯甲烷 为溶剂， 反应 48.0h， 以89%的产率得到1-硫杂螺[4.4]壬烷-6-酮
  参考文献：
  名称：

  Paquette, Leo A.; Dullweber, Uta; Branan, Bruce M., Heterocycles, 1994, vol. 37, # 1, p. 187 - 192

  摘要：

  DOI：

文献信息

• Resolution and Absolute Configurational Assignments to 1-Oxa- and 1-Thia-6-ketospiro[4.4]nonanyl Platforms
  作者：Leo A. Paquette、James C. Lanter、Dafydd R. Owen、Fabrizio Fabris、Richard Todd Bibart、Miriam Alvarez

  DOI：10.3987/com-00-s(i)8

  日期：——
• Analysis of the Conformational Nature, Resolvability, and Thermal Racemization of Hetero 2,3-Dispiro Cyclohexanones. The Weighting of Carbonyl/C-X Stabilization Relative to the Electronic Interaction between the Vicinal Electronegative Substituents
  作者：Leo A. Paquette、Bruce M. Branan、Dirk Friedrich、Scott D. Edmondson、Robin D. Rogers

  DOI：10.1021/ja00081a010

  日期：1994.1

  A series of hetero 2,3-dispiro cyclohexanones has been prepared. The conformations of the syn and anti isomers were assessed in the solid state, in solution, and in the gas phase (the latter by molecular mechanics calculations). The results are discussed in the light of steric, dipole, and gauche interactions; steric contributions give evidence of controlling DELTAG(eq). On a different front, the syn/anti pairs were found to interconvert when heated in the presence of a catalytic amount of acid. Three representative examples of these chiral molecules were resolved and complete racemization was observed to result under the conditions of equilibration. A push-pull fragmentation of the cyclohexanone ring is proposed to account for these observations, with the tethered oniom ion-enol pair reclosing to reconstitute the original, although stereochemically scrambled, structure. The intervention of the thionium ion intermediates is less thermodynamically favorable than that of oxonium ions, as expected.
• Paquette Leo A., Branan Bruce M., Friedrich Dirk, Edmondson Scott D., Rog+, J. Amer. Chem. Soc, 116 (1994) N 2, S 506-513
  作者：Paquette Leo A., Branan Bruce M., Friedrich Dirk, Edmondson Scott D., Rog+

  DOI：——

  日期：——
• Studies of π-diastereofacial selectivity: Spiro 2-tetrahydrofuran and 2-tetrahydrothiophene ketones
  作者：Martin Dimitroff、Alex G Fallis

  DOI：10.1016/s0040-4039(98)00407-9

  日期：1998.4

  The facial influence and synthetic utility of oxygen, sulfur and carbon atoms adjacent to the ketone in the series of alpha-spiro ketones 2, 3, and 4 upon nucleophilic addition has been examined. Addition to the carbonyl group displayed a preference for attack anti to the heteroatom in competition with carbon in synthetically useful ratios. Hydride reduction of 2 with chelating reagents (NaBH4, LiAlH4 etc.) reversed this facial preference. (C) 1998 Elsevier Science Ltd. All rights reserved.
• 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。