(1R)-10-methylthiocamphorthione | 186391-68-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: (1R)-10-methylthiocamphorthione
• 英文别名: (1R,4R)-7,7-dimethyl-1-(methylsulfanylmethyl)bicyclo[2.2.1]heptane-2-thione
• CAS: 186391-68-4
• 化学式: C₁₁H₁₈S₂
• 分子量: 214.396
• InChiKey: OWPMBMJNCBVRFM-LDYMZIIASA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  57.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (1R)-10-methylthiocamphorthione 在 二异丁基氢化铝 作用下， 以 乙醚 、 正己烷 为溶剂， 反应 288.0h， 以70%的产率得到[(1S,2R)-7,7-dimethyl-1-methylsulfanylmethylbicyclo[2.2.1]heptane-2-thiol]
  参考文献：
  名称：

  New camphor-derived sulfur chiral controllers: Synthesis of (2R-exo)-10-methylthio-2-bornanethiol and (2R-exo)-2,10-bis(methylthio)bornane

  摘要：

  An efficient preparation of two camphor-derived controllers [(2R-exo)-10-methylthio-2-bornanethiol 1b and (2R-exo)-2,10-bis(methylthio)bornane 2] potentially useful as a ligands or chiral auxiliaries in asymmetric synthesis is described. Both compounds have been prepared starting from (1S)-camphor-10-thiol 3. Alkylation of this thiol with sodium methoxide and methyl iodide afforded 10-methylthiocamphor 8. Conversion of 8 into the corresponding thioketone 9 with the Lawesson's reagent followed by the stereoselective reduction with DIBAL-H at low temperature yielded (2R-exo)-10-methylthio-2-bornanethiol 1b in good yield. (2R-exo)-2,10-bis(Methylthio)bornane 2 could be obtained by alkylation of 1b with sodium methoxide and methyl iodide. Copyright (C) 1996 Elsevier Science Ltd.

  DOI：

  10.1016/s0957-4166(96)00463-6
• 作为产物：
  描述：

  (1S,4R)-camphor-10-thiol 在 劳森试剂 、 sodium methylate 作用下， 以 甲醇 、 甲苯 为溶剂， 生成 (1R)-10-methylthiocamphorthione
  参考文献：
  名称：

  使用樟脑衍生的螯合硫醇作为手性控制器的不对称Pauson-Khand反应。

  摘要：

  已开发了一种从（1S）-樟脑10硫醇制备对映体纯的10-（R-硫基）-2-exo-降冰片烷硫醇的简便方法。这些硫醇的乙炔基衍生物通过螯合的二钴二羰基五羰基络合物的中间体在与降冰片烯和降冰片二烯的Pauson-Khand反应中具有出色的非对映选择性（高达98：2）。从预形成的螯合配合物开始的热反应条件比采用原位生成螯合中间体的N-氧化物促进的运行更好。通过包括缀合物加成，碘化sa促进的手性助剂的裂解和逆狄尔斯-阿尔德反应组成的方案详细说明了相应的加合物，以得到高对映体纯度的4-取代的2-环戊烯酮。

  DOI：

  10.1021/jo015790p

文献信息

• Asymmetric Pauson−Khand Reactions Using Camphor-Derived Chelating Thiols as Chiral Controllers
  作者：Iolanda Marchueta、Elvira Montenegro、Dmitri Panov、Marta Poch、Xavier Verdaguer、Albert Moyano、Miquel A. Pericàs、Antoni Riera

  DOI：10.1021/jo015790p

  日期：2001.9.1

  (1S)-camphor-10-thiol has been developed. The ethynyl derivatives of these thiols gave excellent diastereoselectivities (up to 98:2) in Pauson-Khand reactions with norbornene and norbornadiene through the intermediacy of a chelated dicobalt pentacarbonyl complex. Thermal reaction conditions starting from the preformed chelated complex gave better results than N-oxide-promoted runs with in situ generation of

  已开发了一种从（1S）-樟脑10硫醇制备对映体纯的10-（R-硫基）-2-exo-降冰片烷硫醇的简便方法。这些硫醇的乙炔基衍生物通过螯合的二钴二羰基五羰基络合物的中间体在与降冰片烯和降冰片二烯的Pauson-Khand反应中具有出色的非对映选择性（高达98：2）。从预形成的螯合配合物开始的热反应条件比采用原位生成螯合中间体的N-氧化物促进的运行更好。通过包括缀合物加成，碘化sa促进的手性助剂的裂解和逆狄尔斯-阿尔德反应组成的方案详细说明了相应的加合物，以得到高对映体纯度的4-取代的2-环戊烯酮。
• New camphor-derived sulfur chiral controllers: Synthesis of (2R-exo)-10-methylthio-2-bornanethiol and (2R-exo)-2,10-bis(methylthio)bornane
  作者：Elvira Montenegro、Raouf Echarri、Carmen Claver、Sergio Castillón、Albert Moyano、Miquel A Pericàs、Antoni Riera

  DOI：10.1016/s0957-4166(96)00463-6

  日期：1996.12

  An efficient preparation of two camphor-derived controllers [(2R-exo)-10-methylthio-2-bornanethiol 1b and (2R-exo)-2,10-bis(methylthio)bornane 2] potentially useful as a ligands or chiral auxiliaries in asymmetric synthesis is described. Both compounds have been prepared starting from (1S)-camphor-10-thiol 3. Alkylation of this thiol with sodium methoxide and methyl iodide afforded 10-methylthiocamphor 8. Conversion of 8 into the corresponding thioketone 9 with the Lawesson's reagent followed by the stereoselective reduction with DIBAL-H at low temperature yielded (2R-exo)-10-methylthio-2-bornanethiol 1b in good yield. (2R-exo)-2,10-bis(Methylthio)bornane 2 could be obtained by alkylation of 1b with sodium methoxide and methyl iodide. Copyright (C) 1996 Elsevier Science Ltd.