4-(1-Methylethyl)-3-<(phenylthio)methyl>-1-oxetan-2-one | 135638-66-3

• 分子结构分类: 有机化合物 - 有机硫化合物 - 硫醚类
• 英文名称: 4-(1-Methylethyl)-3-<(phenylthio)methyl>-1-oxetan-2-one
• 英文别名: 3-(phenylsulfanylmethyl)-4-propan-2-yloxetan-2-one
• CAS: 135638-66-3；135638-67-4
• 化学式: C₁₃H₁₆O₂S
• 分子量: 236.335
• InChiKey: HONFLTYQACIYHN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.98
• 重原子数：
  16.0
• 可旋转键数：
  4.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.46
• 拓扑面积：
  26.3
• 氢给体数：
  0.0
• 氢受体数：
  3.0

反应信息

• 作为反应物：
  描述：

  4-(1-Methylethyl)-3-<(phenylthio)methyl>-1-oxetan-2-one 生成 (Z)-4-Methyl-1-(phenylthio)-2-pentene 、 (E)-4-Methyl-1-(phenylthio)-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 、 苯硫酚 反应 72.0h， 以66%的产率得到4-(1-Methylethyl)-3-<(phenylthio)methyl>-1-oxetan-2-one
  参考文献：
  名称：

  .alpha.-Methylene .beta.-lactones as masked allenes and allene equivalents: some selected chemical transformations

  摘要：

  Selective chemical transformations have been performed on a number of alpha-methylene beta-lactones to illustrate that these highly functionalized heterocycles serve as useful building blocks in organic synthesis. Thus, thermal decarboxylation of these ''masked allenes'' provides a useful regioselective preparation of allenes with a predetermined substitution pattern. Nucleophilic addition takes place at the carbonyl group with ring opening, but free-radical addition, e.g., thiophenol, and electrophilic addition, e.g., bromine, proceed at the exomethylene group with preservation of the beta-lactone ring. [4 + 2] Cycloaddition with cyclopentadiene affords the expected beta-lactones, which on thermal decarboxylation lead to 2-alkylidenenorbornenes. This regio- and stereoselective transformation establishes the alpha-methylene beta-lactones as valuable allene equivalents. The alpha-methylene beta-lactones serve also as dipolarophiles by undergoing readily 1,3-dipolar cycloaddition with diazoalkanes. Reaction with Lawesson's reagent affords a hitherto unknown alpha-methylene beta-(S)-lactone.

  DOI：

  10.1021/jo00020a017

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.
• .alpha.-Methylene .beta.-lactones as masked allenes and allene equivalents: some selected chemical transformations
  作者：Waldemar Adam、Rainer Albert、Ludwig Hasemann、Victor O. Nava Salgado、Bernd Nestler、Eva Maria Peters、Karl Peters、Frank Prechtl、Hans Georg Von Schnering

  DOI：10.1021/jo00020a017

  日期：1991.9

  Selective chemical transformations have been performed on a number of alpha-methylene beta-lactones to illustrate that these highly functionalized heterocycles serve as useful building blocks in organic synthesis. Thus, thermal decarboxylation of these ''masked allenes'' provides a useful regioselective preparation of allenes with a predetermined substitution pattern. Nucleophilic addition takes place at the carbonyl group with ring opening, but free-radical addition, e.g., thiophenol, and electrophilic addition, e.g., bromine, proceed at the exomethylene group with preservation of the beta-lactone ring. [4 + 2] Cycloaddition with cyclopentadiene affords the expected beta-lactones, which on thermal decarboxylation lead to 2-alkylidenenorbornenes. This regio- and stereoselective transformation establishes the alpha-methylene beta-lactones as valuable allene equivalents. The alpha-methylene beta-lactones serve also as dipolarophiles by undergoing readily 1,3-dipolar cycloaddition with diazoalkanes. Reaction with Lawesson's reagent affords a hitherto unknown alpha-methylene beta-(S)-lactone.