(1R,2R,4R)-1-mercaptomethyl-7,7-dimethylbicyclo[2.2.1]heptane-2-thiol | 186391-66-2

• 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,2R,4R)-1-mercaptomethyl-7,7-dimethylbicyclo[2.2.1]heptane-2-thiol
• CAS: 186391-66-2
• 化学式: C₁₀H₁₈S₂
• 分子量: 202.385
• InChiKey: RWTQSUYHBYWYDY-NQMVMOMDSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.04
• 重原子数：
  12.0
• 可旋转键数：
  1.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  0.0
• 氢给体数：
  2.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  (1R,2R,4R)-1-mercaptomethyl-7,7-dimethylbicyclo[2.2.1]heptane-2-thiol 、 碘甲烷 在 三乙胺 作用下， 以 甲醇 为溶剂， 反应 0.5h， 生成 (1R,2R,4R)-7,7-dimethyl-2-methylsulfanyl-1-(methylsulfanylmethyl)bicyclo[2.2.1]heptane
  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：

  Dithiobenzoic acid (1R,4R)-7,7-dimethyl-2-thioxo-bicyclo[2.2.1]hept-1-ylmethyl ester 在 lithium aluminium tetrahydride 作用下， 以 四氢呋喃 、 乙醚 、 苯 为溶剂， 反应 25.0h， 生成 (1R,2R,4R)-1-mercaptomethyl-7,7-dimethylbicyclo[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

文献信息

• Catalytic Asymmetric Epoxidation of Aldehydes. Optimization, Mechanism, and Discovery of Stereoelectronic Control Involving a Combination of Anomeric and Cieplak Effects in Sulfur Ylide Epoxidations with Chiral 1,3-Oxathianes
  作者：Varinder K. Aggarwal、J. Gair Ford、Sílvia Fonquerna、Harry Adams、Ray V. H. Jones、Robin Fieldhouse

  DOI：10.1021/ja9812150

  日期：1998.8.1

  A range of 1,3-oxathianes based on camphorsulfonic acid have been prepared and tested in the catalytic asymmetric epoxidation of carbonyl compounds. It was found that the 1,3-oxathiane derived from acetaldehyde 5b gave the highest yield and enantioselectivity in the epoxidation process. The enantioselectivity was independent of the solvent and metal catalyst used (although yields were dependent on

  已经制备了一系列基于樟脑磺酸的 1,3-氧杂环己烷并在羰基化合物的催化不对称环氧化中进行了测试。发现衍生自乙醛 5b 的 1,3-氧杂环己烷在环氧化过程中具有最高的产率和对映选择性。对映选择性与所使用的溶剂和金属催化剂无关（尽管产率取决于两者）。将最佳条件应用于一系列醛，并观察到良好的对映选择性和非对映选择性。探索了对映选择性的起源，特别是研究了 1,3-氧杂环己烷的氧的作用。因此，制备了基于樟脑磺酸的1,3-氧杂噻吩（衍生自甲醛）的硫和碳类似物（即，1,3-二噻烷和噻烷类似物）。使用这一系列类似物，空间效应被最小化，以便可以研究电子效应。该系列化合物在催化循环中与...