(2S)-2-benzylsulfanylpentanenitrile | 240435-58-9

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2S)-2-benzylsulfanylpentanenitrile
• CAS: 240435-58-9
• 化学式: C₁₂H₁₅NS
• 分子量: 205.324
• InChiKey: RZJSHDMHAMYXJB-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.42
• 拓扑面积：
  49.1
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (2S)-2-benzylsulfanylpentanenitrile 在 lithium aluminium tetrahydride 、 氨 、 sodium 作用下， 以 乙醚 为溶剂， 反应 14.75h， 生成 (S)-1-Amino-pentane-2-thiol
  参考文献：
  名称：

  Stereoselective follow-up reactions of (S)-2-sulfanyl nitriles

  摘要：

  Follow-up reactions of (S)-2-acetylthionitriles (S)-2 and (S)-2-benzylthionitriles (S)-4, respectively, are described. (S)-2-Acetylthionitriles were converted via Pinner reaction to ethyl (S)-2-mercaptocarboxylates (S)-3 almost without racemization. Two routes for the stereoselective preparation of 1,2-amino thiols (S)-5 have been investigated. Hydrogenation of (S)-2 with BH3. THF gave (S)-5 which, however, could not be isolated directly under the reaction conditions, but, by reaction with phosgene in an alkaline medium, the 1,2-amino thiols (S)-5 could be trapped as (S)-5-alkylthiazolidinones (S)-7 in good yields without racemization. (S)-Benzylthioamines (S)-6, derived from (S)-4 by hydrogenation with LiAlH4, were debenzylated with sodium in NH3 to give (S)-5 which were isolated as hydrochlorides with high enantiomeric excesses. Optically active thiomorpholines (S)-12 are accessible starting from (S)-2-(2-hydroxyethylthio)nitriles (S)-10 which are first chlorinated with SOCl2 to yield (S)-2-(2-chloroethylthio)nitriles (S)-11 which after hydrogenation with LiAlH4 cyclize to give thiomorpholines (S)-12. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00155-x
• 作为产物：
  描述：

  [(1R)-1-cyanobutyl] 4-methylbenzenesulfonate 、 苄硫醇 在 potassium carbonate 作用下， 以 乙腈 为溶剂， 反应 40.0h， 以86%的产率得到(2S)-2-benzylsulfanylpentanenitrile
  参考文献：
  名称：

  Stereoselective substitution of (R)-2-(sulfonyloxy)nitriles with sulfur nucleophiles

  摘要：

  Optically active 2-(4-toluenesulfonyloxy)- and (4-nitrobenzenesulfonyloxy)nitriles (R)-3 and (R)-4, which were obtained from (R)-cyanohydrins (R)-2 by sulfonylation, react with sulfur nucleophiles such as potassium thioacetate, potassium ethylxanthogenate, potassium thiocyanate, as well as thioalcohols and thiophenol in a typical S(N)2 manner to give the (S)-2-sulfanyl nitriles (S)-7-9 and (S)-11-13 in good chemical yields and enantiomeric excesses. Even (R)-2-methyl-2-(methanesulfonyloxy)hexanenitrile (R)-6, derived from ketone cyanohydrin (R)-5, reacts with potassium thioacetate to yield (S)-2-acetylthio-2-methylhexanenitrile (S)-10 with 97% ee. (C) 1999 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(99)00154-8

文献信息

• Stereoselective substitution of (R)-2-(sulfonyloxy)nitriles with sulfur nucleophiles
  作者：Franz Effenberger、Sebastian Gaupp

  DOI：10.1016/s0957-4166(99)00154-8

  日期：1999.5

  Optically active 2-(4-toluenesulfonyloxy)- and (4-nitrobenzenesulfonyloxy)nitriles (R)-3 and (R)-4, which were obtained from (R)-cyanohydrins (R)-2 by sulfonylation, react with sulfur nucleophiles such as potassium thioacetate, potassium ethylxanthogenate, potassium thiocyanate, as well as thioalcohols and thiophenol in a typical S(N)2 manner to give the (S)-2-sulfanyl nitriles (S)-7-9 and (S)-11-13 in good chemical yields and enantiomeric excesses. Even (R)-2-methyl-2-(methanesulfonyloxy)hexanenitrile (R)-6, derived from ketone cyanohydrin (R)-5, reacts with potassium thioacetate to yield (S)-2-acetylthio-2-methylhexanenitrile (S)-10 with 97% ee. (C) 1999 Elsevier Science Ltd. All rights reserved.
• Stereoselective follow-up reactions of (S)-2-sulfanyl nitriles
  作者：Sebastian Gaupp、Franz Effenberger

  DOI：10.1016/s0957-4166(99)00155-x

  日期：1999.5

  Follow-up reactions of (S)-2-acetylthionitriles (S)-2 and (S)-2-benzylthionitriles (S)-4, respectively, are described. (S)-2-Acetylthionitriles were converted via Pinner reaction to ethyl (S)-2-mercaptocarboxylates (S)-3 almost without racemization. Two routes for the stereoselective preparation of 1,2-amino thiols (S)-5 have been investigated. Hydrogenation of (S)-2 with BH3. THF gave (S)-5 which, however, could not be isolated directly under the reaction conditions, but, by reaction with phosgene in an alkaline medium, the 1,2-amino thiols (S)-5 could be trapped as (S)-5-alkylthiazolidinones (S)-7 in good yields without racemization. (S)-Benzylthioamines (S)-6, derived from (S)-4 by hydrogenation with LiAlH4, were debenzylated with sodium in NH3 to give (S)-5 which were isolated as hydrochlorides with high enantiomeric excesses. Optically active thiomorpholines (S)-12 are accessible starting from (S)-2-(2-hydroxyethylthio)nitriles (S)-10 which are first chlorinated with SOCl2 to yield (S)-2-(2-chloroethylthio)nitriles (S)-11 which after hydrogenation with LiAlH4 cyclize to give thiomorpholines (S)-12. (C) 1999 Elsevier Science Ltd. All rights reserved.