2,2-Dimethyl-1,3-dioxolane-4-methyl diazoacetate | 162972-95-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 2,2-Dimethyl-1,3-dioxolane-4-methyl diazoacetate
• 英文别名: (2,2-dimethyl-1,3-dioxolan-4-yl)methyl 2-diazoacetate
• CAS: 162972-95-4
• 化学式: C₈H₁₂N₂O₄
• 分子量: 200.194
• InChiKey: GSLNKZGGVBLVKW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.6
• 重原子数：
  14
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  46.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  2,2-Dimethyl-1,3-dioxolane-4-methyl diazoacetate 在 dirhodium(II) tetrakis(caprolactam) 作用下， 以 二氯甲烷 为溶剂， 以60%的产率得到7,7-Dimethyl-2,6,8-trioxaspiro<4.4>nonan-3-one
  参考文献：
  名称：

  Spirolactones from Dirhodium(II)-Catalyzed Diazo Decomposition with Regioselective Carbon-Hydrogen Insertion

  摘要：

  Dirhodium(II) caprolactamate, Rh-2(cap)(4), catalyzes diazo decomposition of cycloalkylmethyl diazoacetates which form spirolactones in moderate to high yield by insertion into a tertiary carbon-hydrogen bond. Similar results are obtained with diazoacetates derived from tetrahydropyran-2-methanol and tetrahydrofurfuryl alcohol but not from cyclopropylmethanol. With tetrahydrofuran-3-ylmethyl diazoacetate, Rh-2(cap)(4) catalysis promotes delta-lactone formation via insertion into the oxygen-activated secondary C-H bond instead of gamma-lactone formation by carbene insertion into the unactivated tertiary C-H bond. However, when both 1,5- and 1,6-positions are activated for insertion by adjacent oxygen atoms, as in (2,2-dimethyl-1,3-dioxolan-4-yl)methyl diazoacetate, five-membered ring formation occurs exclusively in Rh-2(cap)(4)-catalyzed reactions, whereas use of dirhodium(II) acetate leads to both insertion products.

  DOI：

  10.1021/jo00115a018
• 作为产物：
  描述：

  (2,2-dimethyl-1,3-dioxolan-4-yl)methyl 3-oxobutanoate 在 lithium hydroxide 、 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 生成 2,2-Dimethyl-1,3-dioxolane-4-methyl diazoacetate
  参考文献：
  名称：

  Spirolactones from Dirhodium(II)-Catalyzed Diazo Decomposition with Regioselective Carbon-Hydrogen Insertion

  摘要：

  Dirhodium(II) caprolactamate, Rh-2(cap)(4), catalyzes diazo decomposition of cycloalkylmethyl diazoacetates which form spirolactones in moderate to high yield by insertion into a tertiary carbon-hydrogen bond. Similar results are obtained with diazoacetates derived from tetrahydropyran-2-methanol and tetrahydrofurfuryl alcohol but not from cyclopropylmethanol. With tetrahydrofuran-3-ylmethyl diazoacetate, Rh-2(cap)(4) catalysis promotes delta-lactone formation via insertion into the oxygen-activated secondary C-H bond instead of gamma-lactone formation by carbene insertion into the unactivated tertiary C-H bond. However, when both 1,5- and 1,6-positions are activated for insertion by adjacent oxygen atoms, as in (2,2-dimethyl-1,3-dioxolan-4-yl)methyl diazoacetate, five-membered ring formation occurs exclusively in Rh-2(cap)(4)-catalyzed reactions, whereas use of dirhodium(II) acetate leads to both insertion products.

  DOI：

  10.1021/jo00115a018

文献信息

• Conversion of Azides into Diazo Compounds in Water
  作者：Ho-Hsuan Chou、Ronald T. Raines

  DOI：10.1021/ja407822b

  日期：2013.10.9

  compounds are in widespread use in synthetic organic chemistry but have untapped potential in chemical biology. We report on the design and optimization of a phosphinoester that mediates the efficient conversion of azides into diazo compounds in phosphate buffer at neutral pH and room temperature. High yields are maintained in the presence of common nucleophilic or electrophilic functional groups, and reaction

  重氮化合物广泛用于合成有机化学，但在化学生物学中具有未开发的潜力。我们报告了膦酸酯的设计和优化，该酯在中性 pH 值和室温下介导叠氮化物在磷酸盐缓冲液中有效转化为重氮化合物。在常见的亲核或亲电官能团的存在下保持高产率，并且可以通过比色法监测反应进程。由于叠氮基团易于在生物聚合物或其配体中安装和维护，因此这种新的叠氮反应模式在化学生物学中具有重要意义。
• Chemodivergent Staudinger Reactions of Secondary Phosphine Oxides and Application to the Total Synthesis of LL–D05139β Potassium Salt
  作者：Wenjun Luo、Fang Xu、Zhenguo Wang、Jiyan Pang、Zixu Wang、Zhixiu Sun、Aiyun Peng、Xiaohui Cao、Le Li

  DOI：10.1002/anie.202310118

  日期：2023.10.9

  Unprecedented chemodivergent Staudinger reactions of secondary phosphine oxides (SPO) have been developed. Reagent-controlled 1- or 2-nitrogen atom exclusions from azides have been achieved. Conversion of a chiral SPO to a phosphinic amide was stereoretentive, and the potassium salt of natural product LL-D05139β was synthesized for the first time.

  二级氧化膦 (SPO) 史无前例的化学发散施陶丁格反应已经开发出来。已经实现了试剂控制的 1-或 2-氮原子从叠氮化物中的排除。手性SPO立体保留转化为次膦酰胺，首次合成了天然产物LL-D05139β的钾盐。
• Indolization of <i>N</i>-Aryl Tertiary Amines with Diazoacetates by a Single Organophotocatalyst
  作者：Wei Li、Jie Qiu、Hengyuan Li、Wanli Chen、Cheng Hou、Huaifeng Li

  DOI：10.1021/acs.orglett.3c01288

  日期：2023.5.26

  research has focused on using metal carbene reactivity or the innate nucleophilicity of the diazoacetates to create indoles through a traditional two-electron pathway. However, these strategies are constrained by the need for transition metals, oxidants, or substrate prefunctionalization. To overcome the limitations, we report herein an open-shell strategy that utilizes the radical reactivity of diazoacetates

  重氮乙酸酯广泛用于合成高价值的吲哚。以前的研究主要集中在使用金属卡宾反应性或重氮乙酸盐的先天亲核性通过传统的双电子途径产生吲哚。然而，这些策略受到过渡金属、氧化剂或底物预功能化需求的限制。为了克服这些局限性，我们在此报告了一种开壳策略，该策略首次利用重氮乙酸盐的自由基反应性合成吲哚，特别是对于更有价值的 [ a]-环状吲哚。值得注意的是，这种可见光驱动的转化是由单一的有机光催化剂实现的，无需金属或添加剂。初步的机理研究和密度泛函理论计算揭示了一种中继可见光光氧化还原催化过程，该过程可能涉及在使用一种有机光催化剂的单个操作中进行多个离散的光氧化还原催化循环。
• Spirolactones from Dirhodium(II)-Catalyzed Diazo Decomposition with Regioselective Carbon-Hydrogen Insertion
  作者：Michael P. Doyle、Alexey B. Dyatkin

  DOI：10.1021/jo00115a018

  日期：1995.5

  Dirhodium(II) caprolactamate, Rh-2(cap)(4), catalyzes diazo decomposition of cycloalkylmethyl diazoacetates which form spirolactones in moderate to high yield by insertion into a tertiary carbon-hydrogen bond. Similar results are obtained with diazoacetates derived from tetrahydropyran-2-methanol and tetrahydrofurfuryl alcohol but not from cyclopropylmethanol. With tetrahydrofuran-3-ylmethyl diazoacetate, Rh-2(cap)(4) catalysis promotes delta-lactone formation via insertion into the oxygen-activated secondary C-H bond instead of gamma-lactone formation by carbene insertion into the unactivated tertiary C-H bond. However, when both 1,5- and 1,6-positions are activated for insertion by adjacent oxygen atoms, as in (2,2-dimethyl-1,3-dioxolan-4-yl)methyl diazoacetate, five-membered ring formation occurs exclusively in Rh-2(cap)(4)-catalyzed reactions, whereas use of dirhodium(II) acetate leads to both insertion products.