2-allyl 3,4-dimethyl 2,4a-epoxy-1,9,10,10a-tetrahydrophenanthrene-2,3,4-tricarboxylate | 143888-36-2

• 分子结构分类: 有机化合物 - 苯类化合物
• 英文名称: 2-allyl 3,4-dimethyl 2,4a-epoxy-1,9,10,10a-tetrahydrophenanthrene-2,3,4-tricarboxylate
• 英文别名: 2-Allyl 3,4-dimethyl 2,4a-oxy-1,9,20,10a-tetrahydrophenanthrene-2,3,4-tricarboxylate；13-O,14-O-dimethyl 12-O-prop-2-enyl 15-oxatetracyclo[10.2.1.01,10.02,7]pentadeca-2,4,6,13-tetraene-12,13,14-tricarboxylate
• CAS: 143888-36-2
• 化学式: C₂₂H₂₂O₇
• 分子量: 398.412
• InChiKey: NWXXFYWPEUAOAL-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  29
• 可旋转键数：
  8
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.41
• 拓扑面积：
  88.1
• 氢给体数：
  0
• 氢受体数：
  7

反应信息

• 作为产物：
  描述：

  Allyl 2-acetyl-3-<2-(α-tetralonyl)>propionate 在 rhodium(II) acetate dimer 、 三乙胺 、 甲烷磺酰基叠氮化物 作用下， 以 二氯甲烷 、 乙腈 为溶剂， 反应 7.0h， 生成 2-allyl 3,4-dimethyl 2,4a-epoxy-1,9,10,10a-tetrahydrophenanthrene-2,3,4-tricarboxylate
  参考文献：
  名称：

  使用不同羰基的铑类胡萝卜素的环化-环加成反应。突出互动的位置

  摘要：

  当用催化量的羧酸铑（II）处理时，发现一系列3-重氮烷二酮可提供通过捕获羰基内酯中间体而衍生的恶双环二极性环加合物。该反应涉及通过将酮类胡萝卜素分子内环化到相邻酮基的氧原子上来产生1，3-偶极。五环和六环羰基烷基化物以相同的效率形成。还对几种α-重氮酮酸酯的串联环化-环加成级联进行了研究，并且级联序列以高收率进行。当相互作用的酮羰基被亚氨基取代时，铑（II）催化的反应进行得不均匀。相反，在用Rh（II）催化剂处理时，α-重氮酰胺基酯不会进行氮挤出。代替，

  DOI：

  10.1021/jo000378f

文献信息

• Tandem cyclization-cycloaddition reaction of rhodium carbenoids. Studies dealing with intramolecular cycloadditions
  作者：Albert Padwa、Susan F. Hornbuckle、Glen E. Fryxell、Zhijia J. Zhang

  DOI：10.1021/jo00047a032

  日期：1992.10

  A series of 5-alkenyl-1-diazo-2,5-pentanediones, when treated with a catalytic quantity of rhodium(II) acetate, were found to give cycloadducts derived from the intramolecular trapping of a carbonyl ylide intermediate. Tethers of three or four methylenes readily enter into intramolecular cycloaddition, while longer and shorter tethers were reluctant to do so. Alkenes attached to the formally cationic terminus of the carbonyl ylide readily undergo internal cycloaddition if the tether allows for a relatively strain-free transition state. The internal cycloaddition reaction does not occur when the olefinic side chain is attached by means of an ester functionality. Bimolecular trapping experiments established that carbonyl ylide formation occurred, but the dipole does not undergo intramolecular cycloaddition. The inability of these alpha-diazo keto esters to undergo internal cycloaddition is related to conformational factors. The equilibrium between the two possible conformations of the dipole lies predominantly on the side of the Z-isomer. In this orientation, intramolecular dipolar cycloaddition cannot occur, and instead the dipole collapses by means of a proton transfer to give an enol ether.