3-methylene-1-oxaspiro[3.5]nonan-2-one | 135638-62-9

• 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: 3-methylene-1-oxaspiro[3.5]nonan-2-one
• 英文别名: 1-Oxaspiro[3.5]nonan-2-one, 3-methylene-；3-methylidene-1-oxaspiro[3.5]nonan-2-one
• CAS: 135638-62-9
• 化学式: C₉H₁₂O₂
• 分子量: 152.193
• InChiKey: IEXXWUZSVNFHGM-UHFFFAOYSA-N

物化性质

• 沸点：
  300.8±11.0 °C(Predicted)
• 密度：
  1.09±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.9
• 重原子数：
  11
• 可旋转键数：
  0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.67
• 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：

  3-methylene-1-oxaspiro[3.5]nonan-2-one 400.0 ℃ 、13.33 Pa 条件下， 以87%的产率得到环己乙炔
  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
• 作为产物：
  描述：

  环己酮 在 二乙基亚磷酸氢酯 、 硫酸 、 氧气 、 sodium hydride 、 三苯基膦 作用下， 以 氯仿 为溶剂， 反应 38.25h， 生成 3-methylene-1-oxaspiro[3.5]nonan-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

• Ligand‐Controlled Palladium‐Catalyzed Carbonylation of Alkynols: Highly Selective Synthesis of α‐Methylene‐β‐Lactones
  作者：Yao Ge、Fei Ye、Jiawang Liu、Ji Yang、Anke Spannenberg、Haijun Jiao、Ralf Jackstell、Matthias Beller

  DOI：10.1002/anie.202006550

  日期：2020.11.23

  The first general and regioselective Pd‐catalyzed cyclocarbonylation to give α‐methylene‐β‐lactones is reported. Key to the success for this process is the use of a specific sterically demanding phosphine ligand based on N‐arylated imidazole (L11) in the presence of Pd(MeCN)2Cl2 as pre‐catalyst. A variety of easily available alkynols provide under additive‐free conditions the corresponding α‐methylene‐β‐lactones

  报道了第一个普通的和区域选择性的Pd催化的环羰基化反应，生成α-亚甲基-β-内酯。该工艺成功的关键是在Pd（MeCN）2 Cl 2作为预催化剂的情况下，使用基于N-芳基化咪唑（L11）的特定空间要求的膦配体。在无添加剂条件下，各种容易获得的炔醇以中等至良好的产率提供相应的α-亚甲基-β-内酯，具有出色的区域选择性和非对映选择性。这种新方法的适用性通过包括天然产物在内的生物活性分子的直接羰基化得以展示。
• α-Alkylidene-γ-butyrolactone synthesis via one-pot C–H insertion/olefination: substrate scope and the total synthesis of (±)-cedarmycins A and B
  作者：Matthew G. Lloyd、Mariantonietta D'Acunto、Richard J.K. Taylor、William P. Unsworth

  DOI：10.1016/j.tet.2014.09.054

  日期：2015.9

  A system for the synthesis of alpha-alkylidene-gamma-butyrolactones via a one-pot C-H insertion/olefination sequence is described. The process is based on the rhodium catalysed C-H insertion reaction of alpha-diazoa-(diethoxyphosphoryl)acetates. The mild reaction conditions, operational simplicity and ready availability of starting materials are all key features. A wide range of successful reaction systems are reported (41 examples) highlighting the generality of the method. The application of this method in the total synthesis of the natural products (+/-)-cedarmycins A and B is also described. (C) 2014 Elsevier Ltd. All rights reserved.
• Synthesis of allenes via thermal cycloreversion of .alpha.-alkylidene-.beta.-lactones
  作者：Rick L. Danheiser、Yong Mi Choi、Maria Menichincheri、Eric J. Stoner

  DOI：10.1021/jo00054a011

  日期：1993.1

  This paper describes the application of the solution-phase [2 + 2] cycloreversion of alpha-alkylidene-beta-lactones as a practical method for the generation of substituted allenes. Upon heating in dimethylformamide solution at 110-125-degrees-C, these unsaturated beta-lactone derivatives undergo decarboxylation to provide allenes in good to excellent yield. Alpha-alkylidene-beta-lactones are conveniently prepared via the phenylselenylation of beta-lactone enolates followed by oxidative elimination of the resulting alpha-phenylseleno derivatives. The beta-lactone starting materials are synthesized by the addition of thiol ester enolates to ketones and aldehydes according to our recently reported procedure.