4-acetyl-4,10a-epoxy-2,3,3a,4,7,8,9,10,10a,10b-decahydro-1,3,5-trioxo-2-phenyl-1H-pyrrolo<3,4-a>-4H-quinolizine | 126686-07-5

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯烷类
• 英文名称: 4-acetyl-4,10a-epoxy-2,3,3a,4,7,8,9,10,10a,10b-decahydro-1,3,5-trioxo-2-phenyl-1H-pyrrolo<3,4-a>-4H-quinolizine
• 英文别名: 4-acetyl-4,10a-epoxy-2,3,3a,4,7,8,9,10,10a,10b-decahydro-1,3,5-trioxo-2-phenyl-1H-pyrrolo[3,4-a]-4H-quinolizine
• CAS: 126686-07-5；130982-88-6；130982-89-7
• 化学式: C₁₉H₁₈N₂O₅
• 分子量: 354.362
• InChiKey: OAAOZAIUQKOBGF-QABNGEJJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.87
• 重原子数：
  26.0
• 可旋转键数：
  2.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  83.99
• 氢给体数：
  0.0
• 氢受体数：
  5.0

反应信息

• 作为产物：
  描述：

  1-(2-diazo-1,3-dioxobutyl)-2-piperidinone 在 dirhodium tetraacetate 作用下， 以 苯 为溶剂， 生成 4-acetyl-4,10a-epoxy-2,3,3a,4,7,8,9,10,10a,10b-decahydro-1,3,5-trioxo-2-phenyl-1H-pyrrolo<3,4-a>-4H-quinolizine
  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

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。