(E)-(R)-4-hydroxy-1-methyl-2-butenyl phenyl sulfide | 267668-20-2

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: (E)-(R)-4-hydroxy-1-methyl-2-butenyl phenyl sulfide
• 英文别名: (R,E)-4-(phenylthio)pent-2-en-1-ol；trans-(R)-4-phenylthio-2-penten-1-ol；(E,4R)-4-phenylsulfanylpent-2-en-1-ol
• CAS: 267668-20-2
• 化学式: C₁₁H₁₄OS
• 分子量: 194.298
• InChiKey: GAAKNYIADVELKC-BRAIEQGRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.5
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  45.5
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  (E)-(R)-4-hydroxy-1-methyl-2-butenyl phenyl sulfide 在 吡啶 、 lithium aluminium tetrahydride 、 三溴化磷 作用下， 以 四氢呋喃 、 正戊烷 为溶剂， 反应 4.0h， 生成 (E)-(R)-1-methyl-2-butenyl phenyl sulfide
  参考文献：
  名称：

  Fe(II)-Catalyzed Imidation of Allyl Sulfides and Subsequent [2,3]-Sigmatropic Rearrangement. Preparation of α-Branched N-tert-Butyloxycarbonyl (Boc)-Protected N-Allylamines

  摘要：

  Allyl aryl sulfides 1 and 5 were shown to undergo an imidation/[2,3]-sigmatropic rearrangement reaction upon treatment with N-tert-butyloxycarbonyl azide (BocN(3)) and catalytic amounts of FeCl2 in CH2Cl2. The N-Boc-protected N-allyl sulfenamides 3 and 21 were obtained in yields between 48 and 75% (12 examples), Whereas the reaction is well suited for the transformation of alpha-unbranched sulfides to a-branched sulfenamides, the enantiomerically pure alpha-branched sulfides 10 and 13 reacted sluggishly. The corresponding sulfenamides 22 and 23 were obtained in only moderate enantiomeric excess (36-39% eel. A reaction mechanism is proposed that postulates the intermediacy of an N-Boc-substituted Fe(IV)-nitrene complex 14 acting as the imidation reagent in the catalytic cycle. Possible side reactions are discussed. The benzenesulfenamides 3 were further converted into N-Boc-N-allylamines 4 by removal of the phenylsulfanyl group. Bu3SnH in benzene was found to be the reagent of choice for the deprotection of alpha-branched amines that bear a secondary allyl substituent (five examples, 71-93% yield). This method failed for the alpha-branched amines 3i-k with a tertiary allyl substituent. The phenylsulfanyl group was finally removed with P(OEt)(3)/NEt3 in CH2Cl2 (three examples, 43-62% yield).

  DOI：

  10.1021/jo991569p
• 作为产物：
  描述：

  methyl (R)-(+)-2-(phenylthio)propanoate 在 sodium hydride 、 二异丁基氢化铝 作用下， 以 四氢呋喃 、 正己烷 、 二氯甲烷 为溶剂， 反应 1.0h， 生成 (E)-(R)-4-hydroxy-1-methyl-2-butenyl phenyl sulfide
  参考文献：
  名称：

  Fe(II)-Catalyzed Imidation of Allyl Sulfides and Subsequent [2,3]-Sigmatropic Rearrangement. Preparation of α-Branched N-tert-Butyloxycarbonyl (Boc)-Protected N-Allylamines

  摘要：

  Allyl aryl sulfides 1 and 5 were shown to undergo an imidation/[2,3]-sigmatropic rearrangement reaction upon treatment with N-tert-butyloxycarbonyl azide (BocN(3)) and catalytic amounts of FeCl2 in CH2Cl2. The N-Boc-protected N-allyl sulfenamides 3 and 21 were obtained in yields between 48 and 75% (12 examples), Whereas the reaction is well suited for the transformation of alpha-unbranched sulfides to a-branched sulfenamides, the enantiomerically pure alpha-branched sulfides 10 and 13 reacted sluggishly. The corresponding sulfenamides 22 and 23 were obtained in only moderate enantiomeric excess (36-39% eel. A reaction mechanism is proposed that postulates the intermediacy of an N-Boc-substituted Fe(IV)-nitrene complex 14 acting as the imidation reagent in the catalytic cycle. Possible side reactions are discussed. The benzenesulfenamides 3 were further converted into N-Boc-N-allylamines 4 by removal of the phenylsulfanyl group. Bu3SnH in benzene was found to be the reagent of choice for the deprotection of alpha-branched amines that bear a secondary allyl substituent (five examples, 71-93% yield). This method failed for the alpha-branched amines 3i-k with a tertiary allyl substituent. The phenylsulfanyl group was finally removed with P(OEt)(3)/NEt3 in CH2Cl2 (three examples, 43-62% yield).

  DOI：

  10.1021/jo991569p

文献信息

• Regio- and Enantioselective Iridium-Catalyzed Allylation of Thiophenol: Synthesis of Enantiopure Allyl Phenyl Sulfides
  作者：Shengcai Zheng、Ning Gao、Wei Liu、Dongge Liu、Xiaoming Zhao、Theodore Cohen

  DOI：10.1021/ol101915b

  日期：2010.10.15

  A highly regio- and enantioselective allylic alkylation of sodium thiophenoxide has been realized by [Ir(COD)CI](2)/phosphoramidite along with CsF as an additive, producing highly enantioenriched allyl phenyl sulfide compounds with up to 99% ee.
• Fe(II)-Catalyzed Imidation of Allyl Sulfides and Subsequent [2,3]-Sigmatropic Rearrangement. Preparation of α-Branched <i>N</i>-<i>tert</i>-Butyloxycarbonyl (Boc)-Protected <i>N</i>-Allylamines
  作者：Thorsten Bach、Christina Körber

  DOI：10.1021/jo991569p

  日期：2000.4.1

  Allyl aryl sulfides 1 and 5 were shown to undergo an imidation/[2,3]-sigmatropic rearrangement reaction upon treatment with N-tert-butyloxycarbonyl azide (BocN(3)) and catalytic amounts of FeCl2 in CH2Cl2. The N-Boc-protected N-allyl sulfenamides 3 and 21 were obtained in yields between 48 and 75% (12 examples), Whereas the reaction is well suited for the transformation of alpha-unbranched sulfides to a-branched sulfenamides, the enantiomerically pure alpha-branched sulfides 10 and 13 reacted sluggishly. The corresponding sulfenamides 22 and 23 were obtained in only moderate enantiomeric excess (36-39% eel. A reaction mechanism is proposed that postulates the intermediacy of an N-Boc-substituted Fe(IV)-nitrene complex 14 acting as the imidation reagent in the catalytic cycle. Possible side reactions are discussed. The benzenesulfenamides 3 were further converted into N-Boc-N-allylamines 4 by removal of the phenylsulfanyl group. Bu3SnH in benzene was found to be the reagent of choice for the deprotection of alpha-branched amines that bear a secondary allyl substituent (five examples, 71-93% yield). This method failed for the alpha-branched amines 3i-k with a tertiary allyl substituent. The phenylsulfanyl group was finally removed with P(OEt)(3)/NEt3 in CH2Cl2 (three examples, 43-62% yield).