(2S,3S)-2,3-Epoxy-3,7-dimethyl-1-octanol | 108005-72-7

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 环氧化物
• 英文名称: (2S,3S)-2,3-Epoxy-3,7-dimethyl-1-octanol
• 英文别名: ((2S,3S)-3-methyl-3-(4-methylpentyl)oxiran-2-yl)methanol；[(2S,3S)-3-methyl-3-(4-methylpentyl)oxiran-2-yl]methanol
• CAS: 108005-72-7
• 化学式: C₁₀H₂₀O₂
• 分子量: 172.268
• InChiKey: UTZUMWVVZQDNEL-UWVGGRQHSA-N

物化性质

• 沸点：
  226.1±8.0 °C(Predicted)
• 密度：
  0.929±0.06 g/cm3(Temp: 20 °C; Press: 760 Torr)(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.1
• 重原子数：
  12
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  32.8
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S,3S)-2,3-Epoxy-3,7-dimethyl-1-octanol 在 吡啶 、 4-二甲氨基吡啶 、 二甲基硫 、 sodium hydride 、 臭氧 、 溶剂黄146 、 N,N'-二环己基碳二亚胺 、 sodium iodide 、 lithium hexamethyldisilazane 、 锌 作用下， 以 四氢呋喃 、 六甲基磷酰三胺 、 乙醚 、 丙酮 为溶剂， 反应 32.33h， 生成 Methyl (2S,3R,4S)-<2-methyl-2-(4-methylpentyl)-5-oxo-4-(phenylthio)tetrahydrofuran-3-yl>acetate
  参考文献：
  名称：

  Stereoselective Synthesis of Highly Substituted .gamma.-Lactones and Butenolides by Intramolecular Michael Addition of Enantiomerically Enriched .gamma.-[(Phenylthio)acyl]oxy .alpha.,.beta.-Unsaturated Esters

  摘要：

  The synthesis of polysubstituted gamma-lactones by the base-induced cyclization of enantiomerically enriched gamma-((phenylthio)acyl)oxy alpha,beta-unsaturated esters obtained from 2,3-epoxy alcohols is described. The procedure is highly stereoselective and compatible with a wide range of functionalities (ester, tetrahydropyranyl ether, silyl ether, etc.). Varying degrees of substitution, including quaternary centers, in the final gamma-lactone were synthesized with excellent stereoselectivity. Useful functional interconversions were successfully demonstrated, in particular those resulting in butenolides. By the use of AM1 it was concluded that the intramolecular Michael reaction can be described as a kinetically controlled reaction in which the relative stability of the transition states for all possible final configurations led to geometries in agreement with the experimental results.

  DOI：

  10.1021/jo00095a022
• 作为产物：
  描述：

  (2S,3S)-2,3-环氧香叶醇 在 platinum(IV) oxide 氢气 作用下， 以 乙酸乙酯 为溶剂， 反应 4.0h， 以95%的产率得到(2S,3S)-2,3-Epoxy-3,7-dimethyl-1-octanol
  参考文献：
  名称：

  Stereoselective Synthesis of Highly Substituted .gamma.-Lactones and Butenolides by Intramolecular Michael Addition of Enantiomerically Enriched .gamma.-[(Phenylthio)acyl]oxy .alpha.,.beta.-Unsaturated Esters

  摘要：

  The synthesis of polysubstituted gamma-lactones by the base-induced cyclization of enantiomerically enriched gamma-((phenylthio)acyl)oxy alpha,beta-unsaturated esters obtained from 2,3-epoxy alcohols is described. The procedure is highly stereoselective and compatible with a wide range of functionalities (ester, tetrahydropyranyl ether, silyl ether, etc.). Varying degrees of substitution, including quaternary centers, in the final gamma-lactone were synthesized with excellent stereoselectivity. Useful functional interconversions were successfully demonstrated, in particular those resulting in butenolides. By the use of AM1 it was concluded that the intramolecular Michael reaction can be described as a kinetically controlled reaction in which the relative stability of the transition states for all possible final configurations led to geometries in agreement with the experimental results.

  DOI：

  10.1021/jo00095a022

文献信息

• Triflimide-catalysed sigmatropic rearrangement of N-allylhydrazones as an example of a traceless bond construction
  作者：Devon A. Mundal、Christopher T. Avetta、Regan J. Thomson

  DOI：10.1038/nchem.576

  日期：2010.4

  The recognition of structural elements (that is, retrons) that signal the application of specific chemical transformations is a key cognitive event in the design of synthetic routes to complex molecules. Reactions that produce compounds without an easily identifiable retron, by way of either substantial structural rearrangement or loss of the atoms required for the reaction to proceed, are significantly more difficult to apply during retrosynthetic planning, yet allow for non-traditional pathways that may facilitate efficient acquisition of the target molecule. We have developed a triflimide (Tf2NH)-catalysed rearrangement of N-allylhydrazones that allows for the generation of a sigma bond between two unfunctionalized sp3 carbons in such a way that no clear retron for the reaction remains. This new ‘traceless’ bond construction displays a broad substrate profile and should open avenues for synthesizing complex molecules using non-traditional disconnections. A triflimide-catalysed rearrangement of N-allylhydrazones has been developed that allows for the generation of a sigma bond between two unfunctionalized sp3 carbons such that no clear marker remains for how the bond was formed. This traceless bond construction offers new avenues for convergent fragment coupling in synthetic strategies.

  在设计复杂分子的合成路线时，识别结构元素（即逆反应）是应用特定化学转化的关键认知活动。通过大量的结构重排或失去反应进行所需的原子而生成的化合物没有易于识别的重排元素，这种反应在逆合成规划中的应用要困难得多，但却允许通过非传统途径来促进目标分子的高效获取。我们开发了一种由三氟利昂（Tf2NH）催化的 N-烯丙基肼重排反应，它可以在两个未官能化的 sp3 碳之间生成一个西格玛键，从而使反应不再需要明确的重排原子。这种新的 "无痕 "键构造具有广泛的底物特征，为利用非传统断开方式合成复杂分子开辟了道路。我们开发出了一种由三氟甲基甲酰亚胺催化的 N-烯丙基肼重排反应，这种反应可以在两个未官能化的 sp3 碳之间生成一个西格玛键，而且不会留下键是如何形成的明确标记。这种无痕键的构建为合成策略中的聚合片段偶联提供了新的途径。
• SCHMIDT, ULRICH;RESPONDEK, MATHIAS;LIEBERKNECHTI, ALBRECHT;WERNER, JURGEN+, SYNTHESIS,(1989) N, C. 256-261
  作者：SCHMIDT, ULRICH、RESPONDEK, MATHIAS、LIEBERKNECHTI, ALBRECHT、WERNER, JURGEN+

  DOI：——

  日期：——
• Stereoselective Synthesis of Highly Substituted .gamma.-Lactones and Butenolides by Intramolecular Michael Addition of Enantiomerically Enriched .gamma.-[(Phenylthio)acyl]oxy .alpha.,.beta.-Unsaturated Esters
  作者：Carmen M. Rodriguez、Tomas Martin、Miguel A. Ramirez、Victor S. Martin

  DOI：10.1021/jo00095a022

  日期：1994.8

  The synthesis of polysubstituted gamma-lactones by the base-induced cyclization of enantiomerically enriched gamma-((phenylthio)acyl)oxy alpha,beta-unsaturated esters obtained from 2,3-epoxy alcohols is described. The procedure is highly stereoselective and compatible with a wide range of functionalities (ester, tetrahydropyranyl ether, silyl ether, etc.). Varying degrees of substitution, including quaternary centers, in the final gamma-lactone were synthesized with excellent stereoselectivity. Useful functional interconversions were successfully demonstrated, in particular those resulting in butenolides. By the use of AM1 it was concluded that the intramolecular Michael reaction can be described as a kinetically controlled reaction in which the relative stability of the transition states for all possible final configurations led to geometries in agreement with the experimental results.
• A divergent and stereoselective approach to phenolic 1,7-dihydroxy-bisabolane sesquiterpenes: asymmetric total synthesis of (+)-curcutetraol, (+)-sydonol, (+)-sydonic acid, and (+)-7-O-methylsydonic acid
  作者：Stefano Serra、Alessandra A. Cominetti

  DOI：10.1016/j.tetasy.2013.07.011

  日期：2013.9

  The combined use of the Sharpless asymmetric epoxidation, a number of stereospecific chemical transformations, and the 3,5-hexadienoic acid benzannulation protocol allowed us to devise a new, divergent, and stereoselective approach to terpenes with a chiral tertiary hydroxyl group at the ortho-position of a phenol functional group. Accordingly, the natural occurring enantiomeric forms of the bisabolane sesquiterpenes (+)-curcutetraol, (+)-sydonol, (+)-sydonic acid, and (+)-7-O-methylsydonic acid were synthesized with high enantiomeric purity starting from geraniol. The latter two acids were prepared in enantioenriched form for the first time. (C) 2013 Elsevier Ltd. All rights reserved.