N-acetyl-3-diazo-N-methyl-3-oxobutanamide | 126685-99-2

• 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: N-acetyl-3-diazo-N-methyl-3-oxobutanamide
• 英文别名: N-acetyl-2-diazo-N-methyl-3-oxobutanamide
• CAS: 126685-99-2
• 化学式: C₇H₉N₃O₃
• 分子量: 183.167
• InChiKey: YTZXMKMEUNDSJW-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  -0.4
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.43
• 拓扑面积：
  56.4
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  N-acetyl-3-diazo-N-methyl-3-oxobutanamide 在 dirhodium tetraacetate 作用下， 以 苯 为溶剂， 生成 7-acetyl-4,7-epoxy-2,3,3a,4,5,6,7,7a-octahydro-4,5-dimethyl-1,3,6-trioxo-2-phenyl-1H-pyrrolo<3,4-c>pyridine
  参考文献：
  名称：

  Synthesis of nitrogen-containing polycycles via rhodium(II)-induced cyclization-cycloaddition and insertion reactions of N-(diazoacetoacetyl)amides. Conformational control of reaction selectivity

  摘要：

  A series of diazoacetoacetamides, when treated with a catalytic quantity of a rhodium(II) carboxylate, were found to afford products derived from both a carbonyl ylide intermediate and intramolecular C-H insertion. With 3-(N-(diazoacetoacetyl)amino)propanoate derivatives, the rhodium(II)-catalyzed carbenoid reactions exhibit a strong preference for formation of a beta-lactam ring. This is attributed to a conformational preference that juxtaposes the carbenoid center and the less sterically encumbered amide substituent and is consistent with an activating influence on the C-H bond adjacent to the amide nitrogen atom. Carbonyl ylide products derived from carbenoid cyclization onto the ester carbonyl group are also formed, and their relative yields are dependent on electronic influences from the bridging ligands of rhodium(II). Treatment of a series of cyclic diazoimides with rhodium(II) acetate resulted in cyclization of the rhodium carbenoid onto the adjacent imide carbonyl group to produce an isomunchnone dipole. Cyclization onto the imide carbonyl group occurs exclusively even when C-H insertion or aromatic substitution reactions of the carbenoid intermediate are favorable, and this selectivity is also attributed to conformational preferences that juxtapose the carbenoid center and imide carbonyl group. The isomunchnone dipole readily undergoes cycloaddition with several different dipolarophiles to give 1,3-dipolar cycloadducts. When acetylenic dipolarophiles were used as the trapping agents, the initial cycloadducts were found to undergo a [4 + 2]-cycloreversion, producing substituted furans in high yield. The generality of the method was demonstrated by varying the ring size of the cyclic imide. An analogous cyclization-cycloaddition reaction also occurred using diazoacetoacetyl-substituted ureas.

  DOI：

  10.1021/jo00002a058
• 作为产物：
  描述：

  N-acetyl-N-methyl-3-oxobutanamide 在 4-乙酰氨基苯磺酰叠氮 、 三乙胺 作用下， 以 乙腈 为溶剂， 生成 N-acetyl-3-diazo-N-methyl-3-oxobutanamide
  参考文献：
  名称：

  异构体与亚甲基吲哚酮的催化不对称 [3+2] 环加成

  摘要：

  使用手性N , N '-二氧化物/Zn( II ) 络合物作为路易斯酸，通过将羰基原位分子内加成到卡宾铑上，实现了异明酮与亚甲基吲哚酮的有效对映选择性 [3+2] 环加成反应. 以高产率获得了一系列手性氧杂桥联的 3-螺哌啶，具有优异的 dr 和优异的 ee 值。

  DOI：

  10.1039/d1cc03685h

文献信息

• Transition‐Metal‐Free [4+3]‐Cycloaddition of <i>ortho</i> ‐Quinone Methides and Isomünchnones: Catalytic and Diastereoselective Assembly of Oxa‐bridged Oxazocine Scaffolds
  作者：Heather Lam、Zafar Qureshi、Marcus Wegmann、Mark Lautens

  DOI：10.1002/anie.201810760

  日期：2018.12.3

  between an in situ generated ortho‐quinone methide and an isomünchnone to yield oxa‐bridged oxazocine cores, generating N2 and H2O as the sole by‐products. Using only catalytic amounts of camphorsulfonic acid, it is possible to generate both reactive intermediates in one step, eliminating the need for rhodium catalysts generally employed for isomünchnone formation. Spectroscopic data and X‐ray crystallography

  环加成是合成复杂的多环支架的强大过程。本文中，我们公开了在原位生成的邻苯二甲酰甲基甲烷和异麦草酮之间的[4 + 3]-环加成反应，生成草桥连的恶唑啉核，生成N 2和H 2 O作为唯一的副产物。仅使用催化量的樟脑磺酸，就可以在一个步骤中生成两种反应性中间体，从而消除了通常用于异丁香酮形成的铑催化剂的需求。光谱数据和X射线晶体学表明顺式非对映异构体的形成，主要副产物由水合物参与竞争的[4 + 2]-环加成途径。
• Asymmetric Synthesis of Oxa‐Bridged Oxazocines through a Catalytic Rh ^II /Zn ^II Relay [4+3] Cycloaddition Reaction
  作者：Chaoran Xu、Kaixuan Wang、Dawei Li、Lili Lin、Xiaoming Feng

  DOI：10.1002/anie.201910898

  日期：2019.12.16

  oxazocines bearing three chiral carbon centers were synthesized efficiently through a bimetallic catalytic asymmetric tandem reaction of β,γ-unsaturated α-ketoesters with diazoimides. The process contained a rhodium-promoted in situ generation of isomünchnone from diazoimide decomposition, and a [4+3]-cycloaddition of β,γ-unsaturated α-ketoester catalyzed by a chiral N,N'-dioxide-ZnII complex. Ligand-accelerated

  通过β，γ-不饱和α-酮酸酯与重氮酰亚胺的双金属催化不对称串联反应有效地合成了带有三个手性碳中心的桥杂恶唑啉。该过程包括铑由重氮酰亚胺分解原位生成的异丁香酮，以及由手性N，N'-二氧化物-ZnII配合物催化的β，γ-不饱和α-酮酸酯的[4 + 3]-环加成。发现了配体加速催化，并提出了可能的过渡态模型来解释立体选择性的起源。
• Diastereoselective Cascade Cyclization of Diazoimides with Alkylidene Pyrazolones for Preparation of Pyrazole-Fused Oxa-Bridged Oxazocines
  作者：Kuo Wang、Yue Zhang、Lu-Yu Cai、Xiu-Qing Song、Chen Wang、Jia-Rui Zhang、Yi-Fan Pan、Hong-Wu Zhao

  DOI：10.3390/molecules28207021

  日期：——

  Under the catalysis of Rh2(OAc)4 (10 mol%) and binapbisphosphine ligand (±)-L3 (20 mol%) in DCE at 80 °C, the cascade cyclization of diazoimides with alkylidenepyrazolones underwent stereoselectively (dr > 20:1), affording pyrazole-fused oxa-bridged oxazocines in reasonable chemical yields. The chemical structure and relative configuration of title products were firmly identified by X-ray diffraction analysis.

  在 Rh2(OAc)4 (10 mol%)和二巯基二膦配体 (±)-L3 (20 mol%) 的催化下，重氮亚胺与亚烷基吡唑酮在 80 °C下发生了立体选择性 (dr > 20:1)级联环化反应，以合理的化学收率得到了吡唑融合的氧杂桥联噁唑啉。通过 X 射线衍射分析，确定了标题产物的化学结构和相对构型。
• Synthesis of AZA substituted polycycles via rhodium (II) carboxylate induced cyclization of diazoimides
  作者：Albert Padwa、Donald L. Hertzog、Richard L. Chinn

  DOI：10.1016/s0040-4039(00)99326-2

  日期：1989.1
• PADWA, ALBERT;HERTZOG, DONALD L.;CHINN, RICHARD L., TETRAHEDRON LETT., 30,(1989) N1, C. 4077-4080
  作者：PADWA, ALBERT、HERTZOG, DONALD L.、CHINN, RICHARD L.

  DOI：——

  日期：——