(E)-3-methoxycarbonylprop-2-enyl phenyl sulfide | 52938-71-3

• 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)-3-methoxycarbonylprop-2-enyl phenyl sulfide
• 英文别名: trans-4-Phenylthio-2-butensaeure-methylester；methyl (E)-4-phenylsulfanylbut-2-enoate
• CAS: 52938-71-3
• 化学式: C₁₁H₁₂O₂S
• 分子量: 208.281
• InChiKey: SOLDRBFRRZBFFY-VMPITWQZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.6
• 重原子数：
  14
• 可旋转键数：
  5
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.18
• 拓扑面积：
  51.6
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (E)-3-methoxycarbonylprop-2-enyl phenyl sulfide 在 二异丁基氢化铝 作用下， 以 正己烷 、 甲苯 为溶剂， 反应 0.5h， 以46%的产率得到(E)-4-hydroxy-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：

  4-溴-2-丁烯酸甲酯 、 苯硫酚 在 三乙胺 作用下， 以 乙醚 为溶剂， 以82%的产率得到(E)-3-methoxycarbonylprop-2-enyl 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

• Efficient amination of sulfides with a ketomalonate-derived oxaziridine: application to [2,3]-sigmatropic rearrangements of allylic sulfimidesElectronic supplementary information (ESI) available: experimental details and characterisation data. See http://www.rsc.org/suppdata/cc/b2/b201791a/
  作者：Alan Armstrong、Richard S. Cooke

  DOI：10.1039/b201791a

  日期：2002.4.11

  A novel N-Boc-oxaziridine is reported, derived from diethyl ketomalonate, which effects efficient amination of sulfides to sulfimides. The reagent is applied to the [2,3]-sigmatropic rearrangement of allylic sulfimides.

  报道了一种新的N-Boc-恶唑烷，其衍生自酮丁二酸二乙酯，可有效地将硫化物胺化为亚磺酰亚胺。该试剂用于烯丙基硫酰亚胺的[2,3]-σ重排。
• US4233216A
  申请人：——

  公开号：US4233216A

  公开（公告）日：1980-11-11
• 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).