(2R,5R)-2,5-diisopropyltetrahydrothiophene | 1206764-12-6

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 硫杂环戊烷
• 英文名称: (2R,5R)-2,5-diisopropyltetrahydrothiophene
• 英文别名: (2R,5R)-2,5-diisopropyl thiolane；(2R,5R)-2,5-diisopropylthiolane；(2R,5R)-2,5-di(propan-2-yl)thiolane
• CAS: 1206764-12-6
• 化学式: C₁₀H₂₀S
• 分子量: 172.335
• InChiKey: MIYPXPFMWSZQPC-NXEZZACHSA-N

物化性质

• 沸点：
  211.5±8.0 °C(Predicted)
• 密度：
  0.895±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  11
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  25.3
• 氢给体数：
  0
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (2R,5R)-2,5-diisopropyltetrahydrothiophene 、 三氟甲烷磺酸甲酯 以 二氯甲烷 为溶剂， 反应 1.5h， 生成 (2R,5R)-1-methyl-2,5-di(propan-2-yl)thiolan-1-ium;trifluoromethanesulfonate
  参考文献：
  名称：

  通过亚甲基从化ides到亚胺的转移不对称合成末端氮丙啶†

  摘要：

  已经开发了一种新的基于叶立德的方案，用于通过亚甲基转移进行亚胺的不对称叠氮化，涉及使用简单的手性sulf盐和有机强碱。一项系统的研究确定了三异丙基苯基磺酰亚胺为该工艺的最佳底物。出乎意料的是，在C-2和C-5处掺入大体积醚的受阻C 2对称磺酰基盐（以前在相应的环氧化化学中有用）在这些叠氮化反应中通过竞争性消除途径分解。在优化的条件下，发现从（2 R，5 R）-2,5-二异丙基硫杂环戊烷可以介导不对称的亚甲基转移到一系列亚胺上，其ee均具有优异的收率，其ee含量为19％至30％。由于这与在环氧化化学中使用这些相同盐获得的对映体过量水平相似，因此得出结论，如果可以设计出更大体积的sulf盐，在反应条件下耐分解，则可以通过亚甲基转移形成高度对映选择性的氮丙啶可能的。

  DOI：

  10.1039/c3ob27271k
• 作为产物：
  描述：

  (3S,6S)-2,7-dimethyl-3,6-di-O-methanesulfonyloxyoctane 在 sodiumsulfide nonahydrate 作用下， 以 乙醇 为溶剂， 反应 137.0h， 以46%的产率得到(2R,5R)-2,5-diisopropyltetrahydrothiophene
  参考文献：
  名称：

  Catalytic (Asymmetric) Methylene Transfer to Aldehydes

  摘要：

  An investigation into the poor activity of sulfides as catalysts for sulfonium-ylide-mediated methylene transfer to aldehydes has indicated that ylide formation is the problematic catalytic cycle step. Alkylation with traditional electrophiles does not proceed with sufficient efficiency to allow the sulfide to be used catalytically. Methyl triflate rapidly alkylates cyclic thiolanes under mild conditions, allowing their use in efficient aldehyde epoxidation reactions (in conjunction with phosphazene bases) at loadings as low as 10 mol %.

  DOI：

  10.1021/ol902816w
• 作为试剂：
  描述：

  苯甲醛 、 三氟甲烷磺酸甲酯 在 (2R,5R)-2,5-diisopropyltetrahydrothiophene 、 1,8-双二甲氨基萘 、 1-叔丁基-2,2,4,4,4-五(二甲氨基)-2Λ5,4Λ5-连二(磷氮基化合物) 作用下， 以 四氢呋喃 为溶剂， 反应 0.42h， 生成 (R)-环氧苯乙烷 、 (S)-环氧苯乙烷
  参考文献：
  名称：

  Catalytic (Asymmetric) Methylene Transfer to Aldehydes

  摘要：

  An investigation into the poor activity of sulfides as catalysts for sulfonium-ylide-mediated methylene transfer to aldehydes has indicated that ylide formation is the problematic catalytic cycle step. Alkylation with traditional electrophiles does not proceed with sufficient efficiency to allow the sulfide to be used catalytically. Methyl triflate rapidly alkylates cyclic thiolanes under mild conditions, allowing their use in efficient aldehyde epoxidation reactions (in conjunction with phosphazene bases) at loadings as low as 10 mol %.

  DOI：

  10.1021/ol902816w

文献信息

• Explorations into the Potential of Chiral Sulfonium Reagents to Effect Asymmetric Halonium Additions to Isolated Alkenes
  作者：Scott Snyder、Alexandria Brucks、Daniel Treitler、Shu-An Liu

  DOI：10.1055/s-0033-1338865

  日期：——

  While methods for the racemic dihalogenation and halohydroxylation of alkenes have been known for decades, enantioselective variants of these processes remain elusive. Initial attempts were made to overcome this long-standing challenge by exploring the potential of chiral, crystalline, sulfur-derived halonium reagents to accomplish the asymmetric dichlorination and iodohydroxylation of 1,2-dihydronaphthalene. Asymmetric dichlorination of this substrate was achieved in 57% yield and 14% enantiomeric excess (ee), but asymmetric iodohydroxylation was much more successful, giving 67% yield and 63% ee. Thorough studies were made of these processes, including investigation of various chiral sulfide derivatives, their substrate scopes, and the reaction conditions.