4-Methyl-3-methyleneoxetan-2-one | 117203-16-4

• 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: 4-Methyl-3-methyleneoxetan-2-one
• 英文别名: 4-Methyl-3-methylene-1-oxetan-2-one；4-methyl-3-methylideneoxetan-2-one
• CAS: 117203-16-4
• 化学式: C₅H₆O₂
• 分子量: 98.1014
• InChiKey: ABPAZYHRDOVNLH-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  7
• 可旋转键数：
  0
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.4
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  4-Methyl-3-methyleneoxetan-2-one 以 乙醚 为溶剂， 生成 (R)-hydroxy-2-methylene-butyric acid methyl ester
  参考文献：
  名称：

  脂肪酶催化不对称酯交换反应的动力学拆分酶法制备旋光性α-亚甲基β-内酯

  摘要：

  在有机介质中，脂肪酶催化的外消旋α-亚甲基β-内酯1与苯甲醇的不对称酯交换反应提供了旋光性β-内酯和相应的β-羟基酯2，其对映体过量极多（ee 95-99％）。

  DOI：

  10.1016/s0957-4166(97)00054-2
• 作为产物：
  描述：

  5-Methyl-4-methylene-3-oxo-1,2-dioxolane 在 三苯基膦 作用下， 以 氯仿 为溶剂， 以34%的产率得到4-Methyl-3-methyleneoxetan-2-one
  参考文献：
  名称：

  Synthesis of .alpha.-methylene .beta.-lactones, novel heterocycles

  摘要：

  Triphenylphosphine deoxygenation of beta-alkyl, beta,beta-dialkyl-, and beta,beta-spirocycloalkyl-substituted alpha-methylene-beta-peroxy lactones 3a-k, which are readily available by photooxygenation of the corresponding alpha,beta-unsaturated carboxylic acids 1, and cyclization of the resulting alpha-methylene-beta-hydroperoxy acids 2 constitute a convenient method for the preparation of a variety of alpha-methylene beta-lactones 5. Alternatively, the alpha-methylene-beta-hydroxy carboxylic acids 4 can be directly cyclized by benzenesulfonyl chloride in pyridine into these novel four-membered ring heterocycles 5.

  DOI：

  10.1021/jo00020a016

文献信息

• α-Methylene-β-lactones as novel allene equivalents: regioselective [4+2] cycloaddition and stereoselective decarboxylation for the introduction of exo-alkylidene functionalities
  作者：Waldemar Adam、Ludwig Hasemann

  DOI：10.1016/0040-4039(91)85032-z

  日期：1991.11

  β-Lactone-capped allene dienophiles afforded with cyclopentadiene spiro-β-lactone as [4+2] cycloadducts, which on thermal decarboxylation gave regio- and stereoselectively E-5-alkylidene 2-norbornenes.

  β-内酯封端的丙二烯亲二烯体与环戊二烯螺-β-内酯一起作为[4 + 2]环加合物提供，其在热脱羧后得到区域和立体选择性的E-5-亚烷基2-降冰片烯。
• 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.
• The Diastereoselective Synthesis of Ester-Functionalized Alkenes through the Stereocontrolled Conjugate Addition (Michael Reaction) of Prochiral Enolates to Chiral .alpha.-Methylene .beta.-Lactones and Thermal Decarboxylation of the Resulting .alpha.-Substituted .beta.-Lactones
  作者：Victor Oswaldo Nava-Salgado、Eva-Maria Peters、Karl Peters、Hans Georg von Schnering、Waldemar Adam

  DOI：10.1021/jo00117a045

  日期：1995.6
• .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.
• Adam, Waldemar; Hasemann, Ludwig; Prechtl, Frank, Angewandte Chemie, 1988, vol. 100, # 11, p. 1594 - 1595
  作者：Adam, Waldemar、Hasemann, Ludwig、Prechtl, Frank

  DOI：——

  日期：——