(R)-S-2-phenylbut-3-en-2-yl methylcarbamothioate | 1371664-49-1

• 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: (R)-S-2-phenylbut-3-en-2-yl methylcarbamothioate
• 英文别名: S-[(2R)-2-phenylbut-3-en-2-yl] N-methylcarbamothioate
• CAS: 1371664-49-1
• 化学式: C₁₂H₁₅NOS
• 分子量: 221.323
• InChiKey: ISFKKOSZVWWSII-GFCCVEGCSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  15
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.25
• 拓扑面积：
  54.4
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为产物：
  描述：

  (-)-(S)-1-Phenylethanethiol 在 正丁基锂 、 sodium hydride 、 丙酸 、 二异丙胺 作用下， 以 四氢呋喃 、 二氯甲烷 、 N,N-二甲基甲酰胺 、 mineral oil 为溶剂， 反应 30.2h， 生成 (R)-S-2-phenylbut-3-en-2-yl methylcarbamothioate
  参考文献：
  名称：

  Intramolecular Vinylation of Secondary and Tertiary Organolithiums

  摘要：

  Deprotonation of benzylic ureas, carbamates, and thiocarbamates bearing N'-alkenyl substituents generates carbanions which undergo intramolecular migration of the alkenyl group to the carbanionic center. Solvolysis of the urea products generates alpha-alkenylated amines. With an enantiomerically pure starting urea, migration proceeds stereospecifically, generating in enantiomerically enriched form products containing allylic quaternary stereogenic centers bearing N. Computational and in situ IR studies suggest that the reaction, formally a nucleophilic substitution at an sp(2) carbon atom, proceeds by a concerted addition-elimination pathway.

  DOI：

  10.1021/ja301591m

文献信息

• Tertiary Thiols from Allylic Thiocarbamates by Tandem Enantioselective [3,3]-Sigmatropic Rearrangement and Stereospecific Arylation
  作者：Gaëlle Mingat、Paul MacLellan、Marju Laars、Jonathan Clayden

  DOI：10.1021/ol5002522

  日期：2014.2.21

  enriched N-aryl allylic thiocarbamates. Formation of an allyllithium derivative promotes intramolecular N to C aryl migration to the position α to sulfur, generally with good stereospecificity. The substrates may themselves be obtained by Pd-catalyzed enantioselective [3,3]-sigmatropic rearrangement of N-aryl O-allyl thiocarbamates. Solvolysis of the product thiocarbamates yields tertiary thiols, which

  对映体富集形式的叔硫醇的合成通过对映体富集的N-芳基烯丙基硫代氨基甲酸酯的锂化来完成。烯丙基锂衍生物的形成促进分子内N至C芳基迁移至α位至硫，通常具有良好的立体特异性。底物本身可以通过N-芳基O-烯丙基硫代氨基甲酸酯的Pd催化的对映选择性[3,3]-σ重排而获得。产物硫代氨基甲酸酯的溶剂化产生叔硫醇，其可以转化为硫化物衍生物。
• Intramolecular Vinylation of Secondary and Tertiary Organolithiums
  作者：Julien Lefranc、Anne M. Fournier、Gaëlle Mingat、Simon Herbert、Tommaso Marcelli、Jonathan Clayden

  DOI：10.1021/ja301591m

  日期：2012.5.2

  Deprotonation of benzylic ureas, carbamates, and thiocarbamates bearing N'-alkenyl substituents generates carbanions which undergo intramolecular migration of the alkenyl group to the carbanionic center. Solvolysis of the urea products generates alpha-alkenylated amines. With an enantiomerically pure starting urea, migration proceeds stereospecifically, generating in enantiomerically enriched form products containing allylic quaternary stereogenic centers bearing N. Computational and in situ IR studies suggest that the reaction, formally a nucleophilic substitution at an sp(2) carbon atom, proceeds by a concerted addition-elimination pathway.