N-tert-butyloxycarbonyl-N-(1-methyl-2-propenyl)benzenesulfenamide | 267668-23-5

• 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: N-tert-butyloxycarbonyl-N-(1-methyl-2-propenyl)benzenesulfenamide
• 英文别名: tert-butyl N-but-3-en-2-yl-N-phenylsulfanylcarbamate
• CAS: 267668-23-5
• 化学式: C₁₅H₂₁NO₂S
• 分子量: 279.403
• InChiKey: RMWZTYCIXUVINA-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.2
• 重原子数：
  19
• 可旋转键数：
  6
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  54.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  N-tert-butyloxycarbonyl-N-(1-methyl-2-propenyl)benzenesulfenamide 在 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 苯 为溶剂， 反应 1.0h， 以93%的产率得到2-甲基-2-丙基3-丁烯-2-基氨基甲酸酯
  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：

  N-BOC-脒三苯基膦 在 正丁基锂 、 间氯过氧苯甲酸 作用下， 以 四氢呋喃 、 二氯甲烷 为溶剂， 反应 20.5h， 生成 N-tert-butyloxycarbonyl-N-(1-methyl-2-propenyl)benzenesulfenamide
  参考文献：
  名称：

  用酮缩酮酸衍生的恶唑烷高效硫化胺：应用于烯丙基硫酰亚胺的[2,3]-σ重排。

  摘要：

  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。

  DOI：

  10.1039/b201791a

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。
• 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).