3-Methylene-4-(1-methylethyl)-1-oxetan-2-one | 117203-18-6

• 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-4-(1-methylethyl)-1-oxetan-2-one
• 英文别名: 3-Methylidene-4-propan-2-yloxetan-2-one
• CAS: 117203-18-6
• 化学式: C₇H₁₀O₂
• 分子量: 126.155
• InChiKey: KXCMQWZXMUOQSU-UHFFFAOYSA-N

物化性质

• 沸点：
  221.6±9.0 °C(Predicted)
• 密度：
  1.00±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.7
• 重原子数：
  9
• 可旋转键数：
  1
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.57
• 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-4-(1-methylethyl)-1-oxetan-2-one 在 二氯乙基铝 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 0.33h， 以61%的产率得到4,5-Dihydro-5,5-dimethyl-3-methylene-(3H)-furan-2-one
  参考文献：
  名称：

  应变驱动的各向异性重排：α-亚甲基-γ-丁内酯的统一环扩环方法

  摘要：

  已经实现了前所未有的应变驱动的α-亚甲基-β-内酯的重整排列，这使得能够有效利用显示出显着结构多样性的各种α-亚甲基-γ-丁内酯。该反应的几个吸引人的特征，包括出色的效率，高立体特异性，可预测的化学选择性和广泛的底物范围，使其成为合成天然或合成来源的含MBL分子的有力工具。实验和计算证据均表明，致各向异性重排的新变体以二元模式进行：虽然异步协同机制最有可能解释了以氢迁移为特征的反应，但在芳基迁移的情况下，涉及involving离子中间体的逐步过程是有利的。

  DOI：

  10.1002/anie.202013169
• 作为产物：
  描述：

  3-Hydroxy-4-methyl-2-methylenepentanoic acid 在 sodium carbonate 、 邻硝基苯磺酰氯 作用下， 以 二氯甲烷 为溶剂， 以327.6 mg的产率得到3-Methylene-4-(1-methylethyl)-1-oxetan-2-one
  参考文献：
  名称：

  Rh(III)-催化 N-氨基定向 C-H 与 3-亚甲基氧杂环丁烷-2-酮偶联用于 1,2-二氢喹啉-3-羧酸合成

  摘要：

  本文提出动态极性分析作为研究静态极性和瞬态极性并揭示扩展反应模式的通用工具。通过这种分析形式，为 Rh(III) 催化的N-氨基定向 C-H 与 3-亚甲基氧杂环丁烷-2-酮的偶联建立了极性匹配，从而有效地获得 1,2-二氢喹啉-3-羧酸。所确定的反应凭借内氧化机制，表现出温和的反应条件（室温）、短的反应时间（2小时）和普遍较高的产物产率。

  DOI：

  10.1021/acs.orglett.3c03610

文献信息

• Lossen Rearrangement vs C–N Reductive Elimination Enabled by Rh(III)-Catalyzed C–H Activation/Selective Lactone Ring-Opening: Chemodivergent Synthesis of Quinolinones and Dihydroisoquinolinones
  作者：Mengyao Bian、Hamdulla Mawjuda、Hui Gao、Huiying Xu、Zhi Zhou、Wei Yi

  DOI：10.1021/acs.orglett.0c03734

  日期：2020.12.18

  An unprecedented Rh(III)-catalyzed cascade C–H activation/Lossen rearrangement of aromatic amides with methyleneoxetanones has been realized along with a tunable C–N bond reductive elimination/trans esterification, giving divergent access to quinolinones and dihydroisoquinolinones via selective ring-opening of the four-membered lactone unit. Combined computational and experimental mechanistic studies

  已经实现了前所未有的Rh（III）催化的亚甲基氧杂环丁烷芳族酰胺级联C–H活化/丢失重排，以及可调节的C–N键还原性消除/反酯化，可通过选择性开环获得对喹啉酮和二氢异喹啉酮的不同途径。四元内酯单元。组合的计算和实验机理研究定义了溶剂参与的独特反应路径，观察到的化学发散的起源以及连接在氧化导向基团上的取代基在调节反应结果中的作用。
• 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。
• Enzymatic preparation of optically active α-methylene β-lactones by lipase-catalyzed kinetic resolution through asymmetric transesterification
  作者：Waldemar Adam、Peter Groer、Chantu R. Saha-Möller

  DOI：10.1016/s0957-4166(97)00054-2

  日期：1997.3

  The lipase-catalyzed asymmetric transesterification of racemic α-methylene β-lactones 1 with benzyl alcohol in organic media afforded the optically active β-lactones and the corresponding β-hydroxy esters 2 in excellent enantiomeric excess (ee 95–99%).

  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％）。
• 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.
• Chemodivergent Couplings of <i>N</i>-Arylureas and Methyleneoxetanones via Rh(III)-Catalyzed and Solvent-Controlled C–H Activation
  作者：Guoxun Zhu、Wendi Shi、Hui Gao、Zhi Zhou、Huacan Song、Wei Yi

  DOI：10.1021/acs.orglett.9b01333

  日期：2019.6.7

  The efficient couplings of diverse N-arylureas and methyleneoxetanones have been realized via Rh(III)-catalyzed and solvent-controlled chemoselective C-H functionalization, which involved the tunable beta-H elimination and beta-O elimination processes, thereby giving divergent access to quinolin-2(1H)-ones and ortho-allylated N-arylureas with broad substrate compatibility and good functional group tolerance. the divergent synthetic utilities of the transformations have also been exemplified by subsequently tandem C-H allylation, unsymmetrical C-H functionalization, alternative reaction mode, as well as removal of the carbamoyl group.