[1-[[1-(Hydroxymethyl)cyclohexyl]disulfanyl]cyclohexyl]methanol | 212574-87-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 有机二硫化物
• 英文名称: [1-[[1-(Hydroxymethyl)cyclohexyl]disulfanyl]cyclohexyl]methanol
• CAS: 212574-87-3
• 化学式: C₁₄H₂₆O₂S₂
• 分子量: 290.491
• InChiKey: ASXBSDDKMVDZIK-UHFFFAOYSA-N

物化性质

• 沸点：
  437.5±18.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.8
• 重原子数：
  18
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  91.1
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  [1-[[1-(Hydroxymethyl)cyclohexyl]disulfanyl]cyclohexyl]methanol 在 吡啶 、 lithium aluminium tetrahydride 、 sulfur 、 N,N-二异丙基乙胺 、 三氯化磷 作用下， 以 乙醚 、 乙腈 、 苯 为溶剂， 反应 13.58h， 生成 5’-O-DMT-N²-isobutyryl-2’-deoxyguanosine-3’-O-(2-thio-4,4-pentamethylene-1,3,2-oxathiaphospholane)
  参考文献：
  名称：

  Deoxyribonucleoside 3‘-O-(2-Thio- and 2-Oxo-“spiro”-4,4-pentamethylene-1,3,2-oxathiaphospholane)s:  Monomers for Stereocontrolled Synthesis of Oligo(deoxyribonucleoside phosphorothioate)s and Chimeric PS/PO Oligonucleotides

  摘要：

  New monomers, 5'-O-DMT-deoxyribonucleoside 3'-O-(2-thio-"spiro"-4,4-pentamethylene-1,3,2-oxathiaphospholane)s, were prepared and used for the stereocontrolled synthesis of PS-Oligos via the oxathiaphospholane approach. These monomers and their Zero analogues were used for the synthesis of "chimeric" constructs (PS/PO-Oligos) possessing phosphate and P-stereodefined phosphorothioate internucleotide linkages. The yield of a single coupling step is approximately 92-95%, and resulting oligomers are free of nucleobase- and sugar-phosphorothioate backbone modifications. Thermal dissociation studies showed that for heteroduplexes formed by [R-P]-, [S-P]-, or [mix]-PS/PO-T-10 with dA(12), dA(30), Or poly(dA), for each template, the melting temperatures, as well as free Gibbs' energies of dissociation process, are virtually equal. Stereochemical evidence derived from crystallographic analysis of one of the oxathiaphospholane monomers strongly supports the participation of pentacoordinate intermediates in the mechanism of the oxathiaphospholane ring-opening condensation.

  DOI：

  10.1021/ja973801j
• 作为产物：
  描述：

  1-[(2-formylcyclohexyl)disulfanyl]cyclohexanecarbaldehyde 在 sodium tetrahydroborate 作用下， 以 乙醇 为溶剂， 反应 0.5h， 以100%的产率得到[1-[[1-(Hydroxymethyl)cyclohexyl]disulfanyl]cyclohexyl]methanol
  参考文献：
  名称：

  Enantioselective Organocatalytic Oxidation of Functionalized Sterically Hindered Disulfides

  摘要：

  The first study on enantioselective oxidation of functionalized sterically hindered disulfides is reported. This study shows that the Shi organocatalytic system using carbohydrate-derived ketone with oxone is superior to the Ellman-Bolm vanadium catalyst in terms of chemical yield and enantioselectivity. Whereas the latter system afforded mostly racemic thiosulfinates in low to moderate yields, the former one afforded thiosulfinates with up to 96% ee.

  DOI：

  10.1021/ol070056z

文献信息

• Nucleoside 3′-<i>O</i>-(2-Oxo-“<i>Spiro</i>”-4.4-Pentamethylene-1.3.2-Oxathiaphospholane)S: Monomers For Stereocontrolled Synthesis Of Oligo(Nucleoside Phosphorothioate/Phosphate)S
  作者：Boleslaw Karwowski、Piotr Guga、Anna Kobylariska、Wojciech J. Stec

  DOI：10.1080/07328319808004710

  日期：1998.9

  Attempts at synthesis of "chimeric" oligonucleotide constructs (PO/PS-Oligos) possessing phosphate and P-stereodefined phosphorothioate internucleotide linkages via combined phosphoramidite/oxathiaphospholane methods were unsuccessful. Therefore, novel monomers for oxathiaphospholane method, namely 5'-O-DMT-deoxyribonucleoside 3'-O-(2-oxo-spiro-4.4-pentamethylene-1.3.2-oxathiaphospholane)s, were prepared and used together with their diastereomerically pure 2-thio analogues for the stereocontrolled synthesis off "chimeric" oligonucleotide constructs (PO/PS-Oligos).
• Deoxyribonucleoside 3‘-<i>O</i>-(2-Thio- and 2-Oxo-“spiro”-4,4-pentamethylene-1,3,2-oxathiaphospholane)s:  Monomers for Stereocontrolled Synthesis of Oligo(deoxyribonucleoside phosphorothioate)s and Chimeric PS/PO Oligonucleotides
  作者：Wojciech J. Stec、Bolesław Karwowski、Małgorzata Boczkowska、Piotr Guga、Maria Koziołkiewicz、Marek Sochacki、Michał W. Wieczorek、Jarosław Błaszczyk

  DOI：10.1021/ja973801j

  日期：1998.7.1

  New monomers, 5'-O-DMT-deoxyribonucleoside 3'-O-(2-thio-"spiro"-4,4-pentamethylene-1,3,2-oxathiaphospholane)s, were prepared and used for the stereocontrolled synthesis of PS-Oligos via the oxathiaphospholane approach. These monomers and their Zero analogues were used for the synthesis of "chimeric" constructs (PS/PO-Oligos) possessing phosphate and P-stereodefined phosphorothioate internucleotide linkages. The yield of a single coupling step is approximately 92-95%, and resulting oligomers are free of nucleobase- and sugar-phosphorothioate backbone modifications. Thermal dissociation studies showed that for heteroduplexes formed by [R-P]-, [S-P]-, or [mix]-PS/PO-T-10 with dA(12), dA(30), Or poly(dA), for each template, the melting temperatures, as well as free Gibbs' energies of dissociation process, are virtually equal. Stereochemical evidence derived from crystallographic analysis of one of the oxathiaphospholane monomers strongly supports the participation of pentacoordinate intermediates in the mechanism of the oxathiaphospholane ring-opening condensation.
• Enantioselective Organocatalytic Oxidation of Functionalized Sterically Hindered Disulfides
  作者：Noureddine Khiar、Siham Mallouk、Victoria Valdivia、Khalid Bougrin、Mohammed Soufiaoui、Inmaculada Fernández

  DOI：10.1021/ol070056z

  日期：2007.3.1

  The first study on enantioselective oxidation of functionalized sterically hindered disulfides is reported. This study shows that the Shi organocatalytic system using carbohydrate-derived ketone with oxone is superior to the Ellman-Bolm vanadium catalyst in terms of chemical yield and enantioselectivity. Whereas the latter system afforded mostly racemic thiosulfinates in low to moderate yields, the former one afforded thiosulfinates with up to 96% ee.