2-butenyl p-methoxyphenyl sulfide

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯酚醚
• 英文名称: 2-butenyl p-methoxyphenyl sulfide
• 英文别名: 1-but-2-enylsulfanyl-4-methoxybenzene
• 化学式: C₁₁H₁₄OS
• 分子量: 194.298
• InChiKey: UDRBTVDZWJVJRP-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.36
• 重原子数：
  13.0
• 可旋转键数：
  4.0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.27
• 拓扑面积：
  9.23
• 氢给体数：
  0.0
• 氢受体数：
  2.0

反应信息

• 作为反应物：
  描述：

  N-重氮基氨基甲酸叔-丁基酯 、 2-butenyl p-methoxyphenyl sulfide 在 iron(II) chloride 作用下， 以 二氯甲烷 为溶剂， 以52%的产率得到N-tert-butyloxycarbonyl-N-(1-methyl-2-propenyl)-p-methoxybenzenesulfenamide
  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：

  1-溴-2-丁烯 、 4-甲氧基苯硫酚 在 乙醇 、 sodium 作用下， 反应 2.0h， 以1.9 g的产率得到2-butenyl p-methoxyphenyl 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

• Chiral (OC)Ru(salen)-catalyzed tandem sulfimidation and [2,3]sigmatropic rearrangement: asymmetric CN bond formation
  作者：Masakazu Murakami、Tsutomu Katsuki

  DOI：10.1016/s0040-4039(02)00603-2

  日期：2002.5

  manner by using (OC)Ru(salen)-catalyzed sulfimidation and the subsequent [2,3]sigmatropic rearrangement: treatment of allyl aryl sulfides with p-toluenesulfonyl azide in the presence of a catalytic amount of (OC)Ru(salen) followed by hydrolysis of the resulting N-allyl-N-arylthio toluenesulfonamides provided N-allyl toluenesulfonamides of high enantiomeric excess.

  通过使用（OC）Ru（salen）催化的亚磺酰亚胺化和随后的[2,3]σ重排：以对甲苯磺酰基叠氮化物处理烯丙基芳基硫化物，以高度对映选择性的方式实现了不对称CN键的形成。催化量的（OC）Ru（salen），然后将所得的N-烯丙基-N-芳硫基甲苯磺酰胺水解，提供了对映体过量很高的N-烯丙基甲苯磺酰胺。
• 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).