4'-Methylspirohept-5-ene-2,3'-oxetan-2'-one> | 135684-12-7

• 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'-Methylspirohept-5-ene-2,3'-oxetan-2'-one>
• 英文别名: Spirobicyclo[2.2.1]hept-2-ene-5,3'-oxetan-2-'one, 4'beta-methyl-；4'-methylspiro[bicyclo[2.2.1]hept-2-ene-5,3'-oxetane]-2'-one
• CAS: 135684-12-7
• 化学式: C₁₀H₁₂O₂
• 分子量: 164.204
• InChiKey: XGKBCZGJBFBWEU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  12
• 可旋转键数：
  0
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.7
• 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'-Methylspirohept-5-ene-2,3'-oxetan-2'-one> 40.0 ℃ 、13.33 Pa 条件下， 以80%的产率得到5-ethylidene-2-norbornene
  参考文献：
  名称：

  α-亚甲基-β-内酯作为新型的烯丙基等效物：用于引入外亚烷基官能团的区域选择性[4 + 2]环加成和立体选择性脱羧

  摘要：

  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。

  DOI：

  10.1016/0040-4039(91)85032-z
• 作为产物：
  描述：

  环戊二烯 、 4-Methyl-3-methyleneoxetan-2-one 以 二氯甲烷 为溶剂， 反应 336.0h， 以48%的产率得到4'-Methylspirohept-5-ene-2,3'-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

• 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。
• .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.