(S)-tert-butyl (S)-3-methyl-5-oxohexanethioate | 354581-93-4

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: (S)-tert-butyl (S)-3-methyl-5-oxohexanethioate
• 英文别名: S-tert-butyl (S)-3-methyl-5-oxohexanethioate；S-tert-butyl (3S)-3-methyl-5-oxohexanethioate
• CAS: 354581-93-4
• 化学式: C₁₁H₂₀O₂S
• 分子量: 216.345
• InChiKey: PAFHZFNMMYGHPC-QMMMGPOBSA-N

物化性质

• 沸点：
  297.8±23.0 °C(Predicted)
• 密度：
  0.989±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  14
• 可旋转键数：
  6
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.82
• 拓扑面积：
  59.4
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (R)-1-(1-萘基)乙胺 、 (S)-tert-butyl (S)-3-methyl-5-oxohexanethioate 在 silver trifluoroacetate 作用下， 以 四氢呋喃 为溶剂， 生成 (3R,1'R)-N-(1'-(α-naphthyl)ethyl)-3-methyl-5-oxohexaneamide 、 (3S,1'R)-N-(1'-(α-naphthyl)ethyl)-3-methyl-5-oxohexaneamide
  参考文献：
  名称：

  Asymmetric Mukaiyama−Michael Addition of Acyclic Enones Catalyzed by allo-Threonine-Derived B-Aryloxazaborolidinones

  摘要：

  [GRAPHICS]O-(2-Naphthoyl)-N-tosyl-L-allo-threonine B-phenyloxazaborolidinone catalyzes the asymmetric Mukaiyama-Michael addition of simple acyclic enones to give adducts of 54-85% ee, 2,6-Diisopropylphenal as an additive is demonstrated to effectively retard the undesirable Si+-catalyzed racemic pathway.

  DOI：

  10.1021/ol016062r
• 作为产物：
  描述：

  S-叔丁基硫代乙酸酯 在 甲基叔丁基醚 、 丙泊酚 、 chiral oxazoborolidinone 、 lithium diisopropyl amide 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 2.0h， 生成 (S)-tert-butyl (S)-3-methyl-5-oxohexanethioate
  参考文献：
  名称：

  Dimethylsilyl Ketene Acetal as a Nucleophile in Asymmetric Michael Reaction:  Enhanced Enantioselectivity in Oxazaborolidinone-Catalyzed Reaction

  摘要：

  Dimethylsilanyl [Me2Si(H)] ketene SO-acetal 6b is an effective nucleophile that retards the undesirable Si+-catalyzed racemic pathway in the oxazaborolidinone-catalyzed asymmetric Michael reaction. Through the further suppression of the Si+-catalyzed pathway by carrying out the reaction in the presence of 2,6-diisopropylphenol and t-BuOMe as additives, enantioselectivity up to 98% ee could be achieved for a variety of acyclic enones.

  DOI：

  10.1021/ol048071g

文献信息

• Enantioselective Synthesis of Bridged- or Fused-Ring Bicyclic Ketones by a Catalytic Asymmetric Michael Addition Pathway
  作者：Duan Liu、Sungwoo Hong、E. J. Corey

  DOI：10.1021/ja063332y

  日期：2006.6.1

  Efficient methodology has been developed for the conjugate addition of ketene acetals to cyclic alpha,beta-enones. The chiral adducts allow access to fused- or bridged-ring structures such as those shown.

  已开发出将烯酮缩醛共轭加成到环状 α、β-烯酮的有效方法。手性加合物允许访问稠环或桥环结构，如所示。
• Enantioselective Lewis Acid-Catalyzed Mukaiyama−Michael Reactions of Acyclic Enones. Catalysis by <i>a</i><i>llo</i>-Threonine-Derived Oxazaborolidinones
  作者：Xiaowei Wang、Shinya Adachi、Hiroyoshi Iwai、Hiroshi Takatsuki、Katsuhiro Fujita、Mikako Kubo、Akira Oku、Toshiro Harada

  DOI：10.1021/jo035379x

  日期：2003.12.1

  Mukaiyama-Michael reaction of acyclic enones with a trimethylsilyl ketene S,O-acetal in high enantioselectivity. A range of alkenyl methyl ketones is successfully employed as Michael acceptors affording ee values of 85-90% by using 10 mol % of the catalyst. The use of 2,6-diisopropylphenol and tert-butyl methyl ether as additives is found to be essential to achieve high enantioselectivity in these reactions.

  异苏氨酸衍生的O-芳酰基-B-苯基-N-甲苯磺酰基-1,3,2-氧杂硼硼烷-5-酮1g，n催化无环烯酮与三甲基甲硅烷基乙烯酮S，O-乙缩醛的不对称Mukaiyama-Michael反应具有高对映选择性。通过使用10 mol％的催化剂，一系列烯基甲基酮被成功用作Michael受体，ee值为85-90％。已发现使用2，6-二异丙基苯酚和叔丁基甲基醚作为添加剂对于在这些反应中实现高对映选择性是必不可少的。根据阻滞Si（+）催化的外消旋途径来讨论添加剂的作用，这会严重恶化不对称Mukaiyama-Michael反应的对映选择性。基于催化剂结构与对映选择性之间的相关性，提出了一种不对称诱导的工作模型。
• Asymmetric Mukaiyama−Michael Addition of Acyclic Enones Catalyzed by <i>a</i><i>llo</i>-Threonine-Derived <i>B</i>-Aryloxazaborolidinones
  作者：Toshiro Harada、Hiroyoshi Iwai、Hiroshi Takatsuki、Katsuhiro Fujita、Mikako Kubo、Akira Oku

  DOI：10.1021/ol016062r

  日期：2001.6.1

  [GRAPHICS]O-(2-Naphthoyl)-N-tosyl-L-allo-threonine B-phenyloxazaborolidinone catalyzes the asymmetric Mukaiyama-Michael addition of simple acyclic enones to give adducts of 54-85% ee, 2,6-Diisopropylphenal as an additive is demonstrated to effectively retard the undesirable Si+-catalyzed racemic pathway.
• Dimethylsilyl Ketene Acetal as a Nucleophile in Asymmetric Michael Reaction:  Enhanced Enantioselectivity in Oxazaborolidinone-Catalyzed Reaction
  作者：Toshiro Harada、Shinya Adachi、Xiaowei Wang

  DOI：10.1021/ol048071g

  日期：2004.12.1

  Dimethylsilanyl [Me2Si(H)] ketene SO-acetal 6b is an effective nucleophile that retards the undesirable Si+-catalyzed racemic pathway in the oxazaborolidinone-catalyzed asymmetric Michael reaction. Through the further suppression of the Si+-catalyzed pathway by carrying out the reaction in the presence of 2,6-diisopropylphenol and t-BuOMe as additives, enantioselectivity up to 98% ee could be achieved for a variety of acyclic enones.