1-methylsulfanyl-cyclohexanecarboxaldehyde | 181060-03-7

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 1-methylsulfanyl-cyclohexanecarboxaldehyde
• 英文别名: 1-(methylthio)cyclohexanecarbaldehyde；Cyclohexanecarboxaldehyde, 1-(methylthio)-；1-methylsulfanylcyclohexane-1-carbaldehyde
• CAS: 181060-03-7
• 化学式: C₈H₁₄OS
• 分子量: 158.265
• InChiKey: WWQJSZPBYVUFRR-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• 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-methylsulfanyl-cyclohexanecarboxaldehyde 在 lithium aluminium tetrahydride 、 对甲苯磺酰氯 、 lithium diisopropyl amide 作用下， 以 吡啶 、 乙醚 为溶剂， 反应 2.0h， 生成 (2RS,3SR)-1-Cyclohexenyl-2-methyl-3-methylsulfanylpropanol
  参考文献：
  名称：

  Efficient alkylsulfanyl (SMe, SEt and SCH2Ph) and sulfanyl (SH) migration in the stereospecific synthesis of substituted tetrahydrofurans

  摘要：

  Treatment of a series of 4-RS-1,3-diols (R=Me, Et, Bn and H) with TsOH in CH2Cl2 gives substituted tetrahydrofurans. We discuss the scope of this reaction using structural variation of the migrating (RS) substitutent All reactions proceeed in high yield and give synthetically useful products. Copyright (C) 1996 Elsevier Science Ltd

  DOI：

  10.1016/0040-4039(96)00946-x
• 作为产物：
  描述：

  环己甲酸乙酯 在 lithium aluminium tetrahydride 、 二甲基亚砜 、 二异丙胺 、 三氟乙酸酐 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 乙醚 、 二氯甲烷 为溶剂， 反应 6.17h， 生成 1-methylsulfanyl-cyclohexanecarboxaldehyde
  参考文献：
  名称：

  Do the Electronic Effects of Sulfur Indeed Control the π-Selectivity of γ-Sulfenyl Enones? An Investigation

  摘要：

  The electronic effects of sulfur in gamma-sulfenyl enones are not transmitted to the carbonyl carbon through the pi bond as reported previously. The diastereoselectivity is rather controlled by a combination of several other factors. The steric effects arising from the substituents on the sulfur atom and the gamma-carbon and the bulk of the nucleophile constitute the major control elements.

  DOI：

  10.1021/jo034608c

文献信息

• Rhodium-catalyzed α-methylthiolation reaction of unactivated ketones using 1,2-diphenyl-2-methylthio-1-ethanone for the methylthio transfer reagent
  作者：Mieko Arisawa、Fumihiko Toriyama、Masahiko Yamaguchi

  DOI：10.1016/j.tet.2011.01.071

  日期：2011.3

  RhH(PPh3)4, 1,2-bis(diphenylphosphino)ethane (dppe), and dimethyl disulfide, ketones without α-activating groups were α-methylthiolated with 1,2-diphenyl-2-methylthio-1-ethanone giving α-methylthio ketones. The reaction of unsymmetrical ketones proceeded at the more substituted carbons. The initial formation of kinetic α-methylthiolated products followed by their rearrangement to thermodynamic products was

  在催化量的RhH的（PPH的存在3）4，1,2-双（二苯基膦基）乙烷（dppe），和二甲基二硫醚，没有α-活化基团进行了酮α-methylthiolated用1,2-二苯基-2-甲硫基-1-乙酮生成α-甲硫基酮。不对称酮的反应在更多取代的碳上进行。在α-苯基酮的反应中观察到了动力学α-甲基硫醇化产物的最初形成，然后重排为热力学产物。在这些条件下，醛，苯乙酸酯和苯乙腈也被α-甲基硫醇化。
• Scope and limitations of the [1,2]-alkylsulfanyl (SMe, SEt and SCH2Ph) and sulfanyl (SH) migration in the stereospecific synthesis of substituted tetrahydrofurans †
  作者：Jason Eames、Nikolai Kuhnert、Stuart Warren

  DOI：10.1039/b007284m

  日期：——

  dichloromethane gives stereospecifically substituted tetrahydrofurans via a [1,2]-SR shift in near quantitative yield. We comment on the structural variation of the migrating (RS) substituent and that of the migration origin and terminus on the outcome of the title reaction. We also report on the surprising similarity between an alkylsulfanyl (RS) and sulfanyl (SH) migrating group.

  一系列4-RS-1,3-二醇（R = Me，Et，Bn和H）的酸催化重排 甲苯-对磺酸 在 二氯甲烷通过[1,2] -SR位移以接近定量的产率得到立体定向取代的四氢呋喃。我们评论了迁移（RS）取代基的结构变化以及迁移起点和终点在标题反应结果上的变化。我们还报告了烷基硫烷基（RS）与硫烷基 （SH）迁移组。
• Do the Electronic Effects of Sulfur Indeed Control the π-Selectivity of γ-Sulfenyl Enones? An Investigation
  作者：Veejendra K. Yadav、K. Ganesh Babu、Masood Parvez

  DOI：10.1021/jo034608c

  日期：2004.5.1

  The electronic effects of sulfur in gamma-sulfenyl enones are not transmitted to the carbonyl carbon through the pi bond as reported previously. The diastereoselectivity is rather controlled by a combination of several other factors. The steric effects arising from the substituents on the sulfur atom and the gamma-carbon and the bulk of the nucleophile constitute the major control elements.
• Efficient alkylsulfanyl (SMe, SEt and SCH2Ph) and sulfanyl (SH) migration in the stereospecific synthesis of substituted tetrahydrofurans
  作者：Jason Eames、Ray V.H Jones、Stuart Warren

  DOI：10.1016/0040-4039(96)00946-x

  日期：1996.7

  Treatment of a series of 4-RS-1,3-diols (R=Me, Et, Bn and H) with TsOH in CH2Cl2 gives substituted tetrahydrofurans. We discuss the scope of this reaction using structural variation of the migrating (RS) substitutent All reactions proceeed in high yield and give synthetically useful products. Copyright (C) 1996 Elsevier Science Ltd