dimethyl iminodicarboxylate | 51216-94-5

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: dimethyl iminodicarboxylate
• 英文别名: dimethyl iminodicarbonate；methyl N-methoxycarbonylcarbamate
• CAS: 51216-94-5
• 化学式: C₄H₇NO₄
• 分子量: 133.104
• InChiKey: UYXGDZUDCPCVLN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  9
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  64.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  dimethyl iminodicarboxylate 在 溴 、 silver(I) acetate 作用下， 以 四氯化碳 为溶剂， 反应 2.5h， 以75%的产率得到methyl N-bromo-N-methoxycarbonylcarbamate
  参考文献：
  名称：

  Hydroxyamination of Olefins Using Br-N-(CO₂Me)₂

  摘要：

  The hydroxyamination reagent Br-N-(CO2Me)(2) underwent Markovnikov addition to various olefins in the presence of catalytic BF3 center dot OEt2 and provides efficient access to aminoalcohols. The reaction provided the trans-1-bromo, 2-N-bis-carbamate adduct stereoisomer in all cases. The resulting adduct underwent cyclization to give an oxazolidinone, which could be readily hydrolyzed to an oxazolidin-2-one or an amino alcohol.

  DOI：

  10.1021/jo502369d
• 作为产物：
  描述：

  在 盐酸 作用下， 生成 dimethyl iminodicarboxylate
  参考文献：
  名称：

  Use of Thiazyl Chlorides, Alkyl Carbamates, and Thionyl Chloride To Fuse 1,2,5-Thiadiazoles to Quinones and To Oxidize, Chlorinate, and Aminate Them

  摘要：

  Thiazyl chlorides in a simple one-step procedure fuse 1,2,5-thiadiazole rings to quinones. So do alkyl carbamates mixed with excess thionyl chloride and pyridine. Evidence is put forward to support the hypothesis that NSCl or a related thiazyl derivative is the reactive species that brings about the transformations. Selenoyl chloride mixed with an alkyl carbamate, pyridine, and quinones similarly gives 1,2,5-selenodiazoloquinones. Thionyl chloride in pyridine chlorinates quinones and oxidizes hydroquinones. 2,3-Dichloro-1,4-quinones with S4N4 or. with alkyl N-sulfinylcarbamates give 1,2,5-thiadiazoloquinones. Quinones and their 2 3-dichloro derivatives with TsNSO in pyridine give betaine derivatives of 2,3-diaminoquinones, which pyrrolidine converts into 2-amino-3(tosylamino)quinones. A unified set of mechanisms is presented that accounts for these transformations.

  DOI：

  10.1021/jo00110a036

文献信息

• Development and Mechanistic Interrogation of Interrupted Chain-Walking in the Enantioselective Relay Heck Reaction
  作者：Sean P. Ross、Ajara A. Rahman、Matthew S. Sigman

  DOI：10.1021/jacs.0c03589

  日期：2020.6.10

  possibility is that the intermediate alkyl-Pd complexes can undergo a "chain-walking" event, to allow for remote functionalization through various termination processes. However, there are few methods to selectively interrupt the chain-walking process at a prescribed location. Herein we demonstrate that a variety of homoallylic protected amines undergo an interrupted enantioselective relay Heck reaction to give

  通过烯烃的核钯反应形成烷基-钯配合物是各种不同反应的切入点。一种可能性是中间体烷基-钯配合物可以经历“链行走”事件，以允许通过各种终止过程进行远程功能化。然而，很少有方法可以在指定位置选择性地中断链式行走过程。在本文中，我们证明了各种同烯丙基保护的胺经历了间断的对映选择性中继 Heck 反应，以产生对映体富集的烯丙基胺产品。通过改变胺保护基团的性质，该方法的选择性可以转向专门产生烯-酰胺产物。为了使这一观察合理化，我们结合实验和计算来研究链行走过程和终止事件的机制。同位素标记实验和计算出的反应途径表明该系统可能处于热力学控制之下，其选择性由链行走过程中遇到的中间体的相对稳定性驱动。这些结果说明烷基-钯配合物的链式行走可以通过改变热力学过程来控制，并为在未来的反应发展中利用这些过程提供了路线图。选择性是由链行走过程中遇到的中间体的相对稳定性驱动的。这些结果说明烷基-钯配合物的链式行走可以通过
• Synthesis, Characterization and Energetic Performance of Oxalyl Diazide, Carbamoyl Azide, and <i>N</i> , <i>N’</i> ‐Bis(azidocarbonyl)hydrazine
  作者：Alexander G. Harter、Thomas M. Klapötke、Jörg Stierstorfer、Michael Voggenreiter、Xiaoqing Zeng

  DOI：10.1002/cplu.202100214

  日期：2021.6

  precursor. Carbamoyl azide (2) could also be obtained from oxalyl diazide via Curtius rearrangement to the reactive isocyanate, followed by reaction with water. Further, different trapping reactions of the isocyanate with hydroxyl (methanol, oxetan-3-ol) and amino (2-amino-5H-tetrazole) functions are described. All products were extensively analyzed using IR, EA, DTA and multinuclear NMR spectroscopy, and

  作为纯化合物，小羰基叠氮化物由于具有高爆炸敏感性和不稳定性而享有不好的声誉。因此，大多数报告的例子都没有得到很好的描述。通过对相应的肼前体进行重氮化反应，得到化合物草酰二叠氮化物( 1 )、氨基甲酰叠氮化物( 2 )以及N , N'-双(叠氮羰基)肼( 3 )。氨基甲酰叠氮化物( 2 )也可以由草酰二叠氮化物通过Curtius重排生成反应性异氰酸酯，然后与水反应而获得。此外，还描述了异氰酸酯与羟基（甲醇、氧杂环丁烷-3-醇）和氨基（2-氨基-5H-四唑）官能团的不同捕获反应。所有产品均使用 IR、EA、DTA 和多核 NMR 光谱进行了广泛分析，并使用单晶 X 射线衍射阐明了晶体结构。此外，还确定了对摩擦和冲击的敏感性，并使用 EXPLO5 代码计算了羰基叠氮化物的能量性能。
• A Stereoselective Synthesis of (<i>Z</i>)-3-Aryl and Alkylmethylidene-1<i>H</i>-isoindolin-1-ones
  作者：Axel Couture、Marc Lamblin、Eric Deniau、Pierre Grandclaudon

  DOI：10.1055/s-2006-926413

  日期：2006.4

  A series of Z-configured (hetero)aryl and alkylmethylideneisoindolin-1-ones has been efficiently prepared by treatment of N-methoxycarbonylisoindolin-1-ones with a base and reaction with selected aldehydes. The parent N-acylated isoindolin-1-ones have been assembled by a Parham-type cyclization of N-(2-iodoarylmethyl)dicarbamates.

  通过用碱处理N-甲氧羰基异吲哚啉-1-酮并与选定的醛反应，可以有效地制备一系列Z型（杂）芳基和烷基亚甲基异吲哚啉-1-酮。母体N-酰基化异吲哚啉-1-酮是通过N-(2-碘芳基甲基)二氨基甲酸酯的帕勒姆型环化反应组装而成的。
• Asymmetric Substitution by Alkynyl Copper Driven Dearomatization and Rearomatization
  作者：Yu‐Ze Sun、Zi‐Yang Ren、Yuan‐Xiang Yang、Yang Liu、Guo‐Qiang Lin、Zhi‐Tao He

  DOI：10.1002/anie.202314517

  日期：2023.11.20

  Catalytic asymmetric transformations by dearomatization have developed into a widely applicable synthetic strategy, but heavily relied on the use of arenes bearing a heteroatom. In this case, the dearomatization is facilitated by the involvement of a p‐orbital electron of the heteroatom. Different from the conventional substrate‐dependent model, here we demonstrate that the activation by a d‐orbital electron of the transition‐metal center can serve as a driving force for dearomatization, and is applied to the development of a novel asymmetric alkynyl copper facilitated remote substitution reaction. A newly modified PyBox chiral ligand enables the construction of valuable diarylmethyl and triarylmethyl skeletons in high enantioselectivities. An unexpected tandem process involving sequential remote substitution/cyclization/1,5‐H shift leads to the formation of the enantioenriched C−N axis. A gram‐scale reaction and various downstream transformations highlight the robustness of this method and the potential transformations of the products. Preliminary mechanistic studies reveal a mononuclear Cu‐catalyzed remote substitution process.

  摘要脱芳烃催化不对称转化已发展成为一种广泛适用的合成策略，但主要依赖于使用带有一个杂原子的烷烃。在这种情况下，杂原子的 p 轨道电子的参与促进了脱芳香化。与传统的底物依赖模型不同，我们在此证明了过渡金属中心 d 轨道电子的激活可以作为脱芳香化的驱动力，并将其应用于新型不对称炔铜促进远程取代反应的开发。一种新修饰的 PyBox 手性配体能够以高对映选择性构建有价值的二芳基甲基和三芳基甲基骨架。一个意想不到的串联过程（包括连续的远程取代/环化/1,5-H 转变）导致了对映体富集的 C-N 轴的形成。克级反应和各种下游转化过程凸显了该方法的稳健性和产物的潜在转化能力。初步的机理研究揭示了一种单核铜催化的远程取代过程。
• Franchimont; Klobbie, Recueil des Travaux Chimiques des Pays-Bas, 1889, vol. 8, p. 285
  作者：Franchimont、Klobbie

  DOI：——

  日期：——