(2R,3S)-2-<(methylsulfanyl)methyl>-3-propyloxirane | 145762-61-4

• 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: (2R,3S)-2-<(methylsulfanyl)methyl>-3-propyloxirane
• 英文别名: <(methylthio)methyl>-(2S,3S)-3-propyloxirane；(-)-2-<(methylthio)methyl>-(2R,3S)-3-propyloxirane；(2R,3S)-2-(methylsulfanylmethyl)-3-propyloxirane
• CAS: 145762-61-4
• 化学式: C₇H₁₄OS
• 分子量: 146.254
• InChiKey: YSCCUDQIZKPALZ-BQBZGAKWSA-N

物化性质

• 沸点：
  198.3±13.0 °C(Predicted)
• 密度：
  0.975±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  9
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  37.8
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2R,3S)-2-<(methylsulfanyl)methyl>-3-propyloxirane 在 碳酸氢钠 作用下， 以 甲醇 、 二氯甲烷 、 溶剂黄146 为溶剂， 反应 7.17h， 生成 (S)-2-((2R,3S)-3-Hydroxy-2-methylsulfanyl-hexylamino)-3-phenyl-propionic acid isopropyl ester
  参考文献：
  名称：

  Addition of amino esters to thiiranium ion intermediates: A novel approach to the synthesis of new potential aminopeptidase inhibitors

  摘要：

  DOI：

  10.1016/0040-4039(95)01741-y
• 作为产物：
  描述：

  (2S,3S)-(-)-3-丙基环氧乙烷甲醇 、 sodium thiomethoxide 在 吡啶 、 对甲苯磺酰氯 作用下， 生成 (2R,3S)-2-<(methylsulfanyl)methyl>-3-propyloxirane
  参考文献：
  名称：

  路易斯酸诱导的 1-Hetero-2,3-Epoxides 重排。单手性硫溴鎓和氮丙啶离子中间体的合成、反应性和合成应用

  摘要：

  2,3-环氧硫化物和2,3-环氧胺通过Sharpless不对称环氧化制备成光学活性形式，均在路易斯酸的诱导下发生重排，分别生成相应的硫铵离子和叠氮离子。这些在原位生成的反应中间体与各种亲核试剂有效反应，如硅化的芳香杂环、酰胺和胺，包括氨基酸衍生物。亚胺可以用作一级胺亲核试剂的合成等价物，这有效地实现了与反应活性硫铵离子中间体的选择性单烷基化。还讨论了这一新方法的应用及其机理研究。

  DOI：

  10.1055/s-1997-3729

文献信息

• Lewis acid induced rearrangement of 2,3-epoxy sulfides; regiospecific trapping of thiiranium ion intermediates with nitrogen heterocycles and amides. Use of imines as nucleophilic equivalents for the selective monoalkylation of primary amines
  作者：Duncan M Gill、Neil A Pegg、Christopher M Rayner

  DOI：10.1016/0040-4020(96)00036-1

  日期：1996.3

  The Lewis acid induced conversion of 2,3-epoxy sulfides into the corresponding 3-trimethylsilyloxy-1,2-thiiranium ions is described. Such intermediates react with silylated nitrogen heterocycles and amides regiospecifically to form 1-substituted-3-hydroxy-2-thioethers in good to moderate yields with full stereochemical control. Exclusive N-alkylation is observed. When simple primary amines are used

  描述了路易斯酸诱导的2，3-环氧硫化物到相应的3-三甲基甲硅烷氧基-1，2-噻吩鎓离子的转化。这样的中间体与甲硅烷基化的氮杂环和区域特异性的酰胺反应，以完全中等的化学控制，以良好至中等的产率形成1-取代的3-羟基-2-硫醚。观察到排他的N-烷基化。当简单的伯胺用作亲核试剂时，仅分离出多烷基化产物。但是，亚胺可以有效地用作伯胺的亲核当量，最初形成的亚胺离子很容易被碱水溶液水解而释放出仲胺，这是伯胺整体选择性单烷基化的产物。
• Reaction of α-amino esters and α-amino ester imines with thiiranium ion intermediates. Application to the synthesis of new potential aminopeptidase inhibitors and mechanistic implications
  作者：Duncan M Gill、Neil A Pegg、Christopher M Rayner

  DOI：10.1016/s0040-4020(97)00060-4

  日期：1997.3

  situ from 2,3-epoxy sulfides, to give an iminium ion which can be readily hydrolysed by aqueous base to liberate a secondary amine, the product of selective monoalkylation of the primary amino group. Overall yields for this process are only moderate, but can be improved by use of α-amino esters themselves as nucleophiles at low temperature. Interesting reactivity profiles of the thiiranium ion intermediates

  衍生自α-氨基酯的亚胺与2,3-环氧硫化物就地生成的噻吩离子反应，生成亚胺离子，该碱离子易于被碱水溶液水解以释放仲胺，该胺是伯氨基选择性单烷基化的产物团体。该方法的总产率仅中等，但是可以通过在低温下将α-氨基酯本身用作亲核试剂来提高。观察到了噻吩鎓离子中间体有趣的反应性概况，并讨论了其对所涉及的反应性中间体性质的影响。从这些反应中获得的产物是用于合成与α-硫磺抑制素和其他已知有效的氨基肽酶抑制剂有关的化合物的模型系统。
• Stereoselective synthesis of 2,3-epoxy sulphoxides.
  作者：Christopher M. Rayner、Man S. Sin、Andrew D. Westwell

  DOI：10.1016/s0040-4039(00)60882-1

  日期：1992.11

  Methods for the diastereoselective preparation of various 2,3-epoxy sulphoxides are described using a double enantioselective oxidation approach. Direct comparisons of the selectivity and efficiency of the Davis and Kagan asymmetric sulphur oxidation procedure are given.

  使用双对映选择性氧化方法描述了各种2,3-环氧亚砜的非对映选择性制备方法。直接比较了戴维斯和卡根不对称硫氧化工艺的选择性和效率。
• Optically active 2,3-epoxy sulfides as precursors to 3-hydroxy-1,2-dithioethers and 3-hydroxy-1-alkenylthioethers
  作者：Ian Forristal、Kevin R. Lawson、Christopher M. Rayner

  DOI：10.1016/s0040-4039(99)01427-6

  日期：1999.9

  Procedures are reported far the conversion of 2,3-epoxysulfides to 3-hydroxy-1,2-dithioethers. Conventional nucleophilic ring opening using a thiolate gives a mixture of products resulting from ring opening at C-2 and C-3, with the latter predominating. With sodium thiolates in DMF a competing beta-elimination process is observed to form 3-hydroxy-1-alkenylthioethers. Alternatively, Lewis acid induced thiiranium ion generation from a 2,3-epoxy sulfide, and nucleophilic ring opening with S-trimethylsilylthiophenol gives 3-hydroxy-1,2-dithioethers with full regio- and stereo-control. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Homochiral 2,3-epoxy sulfides—powerful new synthetic building blocks providing stereoselective access to 2,3-epoxy sulfoxides, 2,3-dihydroxy sulfoxides and (E)-γ-hydroxy-α,β-unsaturated sulfoxides and sulfones. X-Ray molecular structure of rac-(2R*,3R*)-1-[(S*)-phenylsulfinyl] hexane-2,3-diol
  作者：Andrew D. Westwell、Mark Thornton-Pett、Christopher M. Rayner

  DOI：10.1039/p19950000847

  日期：——

  The stereoselective transformation of homochiral 2,3-epoxy sulfoxides into 2,3-epoxy sulfoxides is described. These intermediates undergo elimination under basic reaction conditions to give (E)-gamma-hydroxy-alpha,beta-unsaturated sulfoxides, and under Lewis acidic conditions form novel cyclic sulfoxonium salts which on hydrolysis give 2,3-dihydroxy sulfoxides with excellent stereochemical control. 2,3-Dihydroxy sulfoxides can also be converted into (E)-gamma-hydroxy-alpha,beta-unsaturated sulfoxides by elimination via a cyclic sulfite. The synthesis of (E)-gamma-hydroxy-alpha,beta-unsaturated sulfones by base-catalysed elimination of a 2,3-epoxy sulfone is also described.