spiro<4,7-epoxy-4-methyl-2-phenyl-1,3,6-trioxopseudoisoindole-5,1'-cyclopropane> | 133374-51-3

• 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: spiro<4,7-epoxy-4-methyl-2-phenyl-1,3,6-trioxopseudoisoindole-5,1'-cyclopropane>
• 英文别名: spiro[4,7-epoxy-4-methyl-2-phenyl-1,3,6-trioxopseudoisoindole-5,1'-cyclopropane]；(3aS,4S,7R,7aR)-7-methyl-2-phenylspiro[4,7a-dihydro-3aH-4,7-epoxyisoindole-6,1'-cyclopropane]-1,3,5-trione
• CAS: 133374-51-3
• 化学式: C₁₇H₁₅NO₄
• 分子量: 297.31
• InChiKey: UFFZQRDPXVSCPX-CENBSLRLSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.31
• 重原子数：
  22.0
• 可旋转键数：
  1.0
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.47
• 拓扑面积：
  63.68
• 氢给体数：
  0.0
• 氢受体数：
  4.0

反应信息

• 作为反应物：
  描述：

  1-Diazo-3,3,5-trimethyl-hexane-2,4-dione 、 spiro<4,7-epoxy-4-methyl-2-phenyl-1,3,6-trioxopseudoisoindole-5,1'-cyclopropane> 、 二聚醋酸铑 以63%的产率得到
  参考文献：
  名称：

  PADWA, ALBERT;CHINN, RICHARD L.;HORNBUCKLE, SUSAN F.;ZHI, LIN, TETRAHEDRON LETT., 30,(1989) N 3, C. 301-304

  摘要：

  DOI：
• 作为产物：
  描述：

  N-苯基马来酰亚胺 、 1-acetyl-1-(diazoacetyl)cyclopropane 在 rhodium(II) acetate dimer 作用下， 以 氘代氯仿 为溶剂， 生成 spiro<4,7-epoxy-4-methyl-2-phenyl-1,3,6-trioxopseudoisoindole-5,1'-cyclopropane>
  参考文献：
  名称：

  乙酸铑（II）催化1-重氮烷二酮反应生成环状羰基内酯

  摘要：

  用乙酸铑（II）处理1-重氮烷二酮导致中间体铑类胡萝卜素环化，得到环状羰基叶立德，其容易与各种偶极亲和剂进行双分子偶极环加成。

  DOI：

  10.1016/s0040-4039(00)95185-2

文献信息

• Ionic liquids as a convenient recyclable medium for the generation of transient carbonyl ylides: syntheses of oxa and dioxa-bridged polycyclic systems
  作者：Sengodagounder Muthusamy、Boopathy Gnanaprakasam

  DOI：10.1016/j.tet.2004.11.008

  日期：2005.1

  octanoate or copper(II) acetyl acetonate as catalyst were performed in different imidazole based ionic liquids as solvent. A successful generation of the transient five- or six-membered-ring carbonyl ylides, followed by the 1,3-dipolar cycloaddition with olefin or carbonyl functional groups in ionic liquid is described to furnish the oxa and dioxa-bridged polycyclic systems with high stereoselectivity.

  在不同的以咪唑类离子液体为溶剂的条件下，在乙酸铑（II），辛酸铑（II）或乙酰丙酮铜（II）存在下，α-重氮酮进行串联环化-环加成反应。描述了成功生成瞬态的五元或六元环羰基羰基化物，然后在离子液体中与烯烃或羰基官能团进行1,3-偶极环加成反应，以提供具有高立体选择性的氧杂和二氧杂桥联多环系统。该方法的显着优势是回收铑催化剂，离子液体的重复使用，危险有机溶剂的替代以及由此产生的高立体选择性。
• Tandem cyclization-cycloaddition reaction of rhodium carbenoids. Studies dealing with the geometric requirements of dipole formation
  作者：Albert Padwa、Richard L. Chinn、Susan F. Hornbuckle、Zhijia J. Zhang

  DOI：10.1021/jo00010a019

  日期：1991.5

  The carbenoid intermediate derived by the treatment of several 1-diazobutanediones with rhodium(II) acetate undergoes ready transannular cyclization onto the neighboring keto group to give five-membered ring carbonyl ylides. The dipole derived from ethyl 4-diazo-2-methyl-3-oxobutyrate was found to undergo a rapid proton transfer, producing 5-ethoxy-4-methyl-3-(2H)-furanone. When the position adjacent to the diazo carbonyl group is blocked with two substituent groups, however, smooth 1,3-dipolar cycloaddition occurs. The observed regioselectivity can be nicely accommodated in terms of frontier molecular orbital (FMO) theory. A type II FMO interaction is involved since carbonyl ylides possess one of the smallest HOMO-LUMO energy gaps of common 1,3-dipoles. The rhodium(II)-catalyzed reaction of 1-diazo-6-phenyl-2,6-hexanedione afforded a mixture of products. In addition to the expected cycloadduct, a product derived from the bimolecular addition of the rhodium carbenoid to benzene was obtained. The formation of a mixture of products in this case suggests that entropic factors have sufficiently retarded the rate of intramolecular cyclization so as to allow the bimolecular reaction with benzene to occur. No observable cycloadduct was obtained from the diazohexanedione system, thereby indicating that the longer tether was sufficient to shut down dipole formation.