trans-4-(1-Methylethyl)-3-<<(1-methylethyl)thio>methyl>-1-oxetan-2-one

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: trans-4-(1-Methylethyl)-3-<<(1-methylethyl)thio>methyl>-1-oxetan-2-one
• 英文别名: (3S,4S)-4-propan-2-yl-3-(propan-2-ylsulfanylmethyl)oxetan-2-one
• 化学式: C₁₀H₁₈O₂S
• 分子量: 202.318
• InChiKey: YLKMMXSJWTZAQL-IUCAKERBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  13
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.9
• 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：

  trans-4-(1-Methylethyl)-3-<<(1-methylethyl)thio>methyl>-1-oxetan-2-one 以74%的产率得到(E)-4-Methyl-1-<(1-methylethyl)thio>-2-pentene
  参考文献：
  名称：

  Stereoselective Synthesis of .alpha.-Amino and .alpha.-Thio .beta.-Lactones by Conjugate Addition of Amine and Thiol Nucleophiles to .alpha.-Methylene .beta.-Lactones and Their Decarboxylation to Allylamines and Sulfides

  摘要：

  The stereoselective, conjugate addition of secondary, cyclic amines (pyrrolidine and piperidine) and mercaptans (thiophenol, isopropyl, and benzyl thiols and beta-mercaptoethanol) to alpha-methylene beta-lactones 1 and 2 was investigated. The corresponding alpha-(aminomethyl) and alpha-(thiomethyl) beta-lactones 3-5 and 6-10 were obtained in excellent yields through protonation of the intermediary enolates. In methanol the trans isomers mere the major products, while considerable amounts of the cis isomers were formed in THF and acetone. The decarboxylation of these alpha-aminomethyl and alpha-thiomethyl beta-lactones as neat samples at 180 degrees C produced in excellent yields the corresponding allyl amines and sulfides 11-13 and 14-18 with retention of the initial beta-lactone geometry. This unprecedented sequence of Michael-type addition followed by decarboxylation, in which the alpha-methylene beta-lactones serve as allene equivalents, provides a useful alternative to the Wittig olefination for the preparation of allylic amines and sulfides.

  DOI：

  10.1021/jo00108a019
• 作为产物：
  描述：

  3-Methylene-4-(1-methylethyl)-1-oxetan-2-one 、 异丙硫醇 在 三乙胺 作用下， 以 甲醇 为溶剂， 反应 1.0h， 生成 trans-4-(1-Methylethyl)-3-<<(1-methylethyl)thio>methyl>-1-oxetan-2-one
  参考文献：
  名称：

  Stereoselective Synthesis of .alpha.-Amino and .alpha.-Thio .beta.-Lactones by Conjugate Addition of Amine and Thiol Nucleophiles to .alpha.-Methylene .beta.-Lactones and Their Decarboxylation to Allylamines and Sulfides

  摘要：

  The stereoselective, conjugate addition of secondary, cyclic amines (pyrrolidine and piperidine) and mercaptans (thiophenol, isopropyl, and benzyl thiols and beta-mercaptoethanol) to alpha-methylene beta-lactones 1 and 2 was investigated. The corresponding alpha-(aminomethyl) and alpha-(thiomethyl) beta-lactones 3-5 and 6-10 were obtained in excellent yields through protonation of the intermediary enolates. In methanol the trans isomers mere the major products, while considerable amounts of the cis isomers were formed in THF and acetone. The decarboxylation of these alpha-aminomethyl and alpha-thiomethyl beta-lactones as neat samples at 180 degrees C produced in excellent yields the corresponding allyl amines and sulfides 11-13 and 14-18 with retention of the initial beta-lactone geometry. This unprecedented sequence of Michael-type addition followed by decarboxylation, in which the alpha-methylene beta-lactones serve as allene equivalents, provides a useful alternative to the Wittig olefination for the preparation of allylic amines and sulfides.

  DOI：

  10.1021/jo00108a019

文献信息

• Stereoselective Synthesis of .alpha.-Amino and .alpha.-Thio .beta.-Lactones by Conjugate Addition of Amine and Thiol Nucleophiles to .alpha.-Methylene .beta.-Lactones and Their Decarboxylation to Allylamines and Sulfides
  作者：Waldemar Adam、Victor Oswaldo Nava-Salgado

  DOI：10.1021/jo00108a019

  日期：1995.2

  The stereoselective, conjugate addition of secondary, cyclic amines (pyrrolidine and piperidine) and mercaptans (thiophenol, isopropyl, and benzyl thiols and beta-mercaptoethanol) to alpha-methylene beta-lactones 1 and 2 was investigated. The corresponding alpha-(aminomethyl) and alpha-(thiomethyl) beta-lactones 3-5 and 6-10 were obtained in excellent yields through protonation of the intermediary enolates. In methanol the trans isomers mere the major products, while considerable amounts of the cis isomers were formed in THF and acetone. The decarboxylation of these alpha-aminomethyl and alpha-thiomethyl beta-lactones as neat samples at 180 degrees C produced in excellent yields the corresponding allyl amines and sulfides 11-13 and 14-18 with retention of the initial beta-lactone geometry. This unprecedented sequence of Michael-type addition followed by decarboxylation, in which the alpha-methylene beta-lactones serve as allene equivalents, provides a useful alternative to the Wittig olefination for the preparation of allylic amines and sulfides.