spiro<5-carbomethoxy-4-methyl-7-oxabicyclo<2.2.1>hept-5-en-2-one-3,1'-cyclopropane> | 122889-56-9

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: spiro<5-carbomethoxy-4-methyl-7-oxabicyclo<2.2.1>hept-5-en-2-one-3,1'-cyclopropane>
• 英文别名: spiro<2-carbomethoxy-1-methyl-7-oxabicyclo<2.2.1>-2-hepten-5-one-6,1'-cyclopropane>；Spiro[cyclopropane-1,2'-[7]oxabicyclo[2.2.1]hept[5]ene]-6'-carboxylic acid, 1'-methyl-3'-oxo-, methyl ester；methyl 1-methyl-5-oxospiro[7-oxabicyclo[2.2.1]hept-2-ene-6,1'-cyclopropane]-2-carboxylate
• CAS: 122889-56-9
• 化学式: C₁₁H₁₂O₄
• 分子量: 208.214
• InChiKey: WPIVZURZDRJALN-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.2
• 重原子数：
  15
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.64
• 拓扑面积：
  52.6
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  spiro<5-carbomethoxy-4-methyl-7-oxabicyclo<2.2.1>hept-5-en-2-one-3,1'-cyclopropane> 、 苯 以50%的产率得到
  参考文献：
  名称：

  PADWA, ALBERT;ZHI, LIN;FRYXELL, GLEN E., J. ORG. CHEM., 56,(1991) N, C. 1077-1083

  摘要：

  DOI：
• 作为产物：
  描述：

  1-acetyl-1-(diazoacetyl)cyclopropane 、 丙炔酸甲酯 在 dirhodium tetraacetate 作用下， 以 氯仿 为溶剂， 反应 0.5h， 以58%的产率得到spiro<5-carbomethoxy-4-methyl-7-oxabicyclo<2.2.1>hept-5-en-2-one-3,1'-cyclopropane>
  参考文献：
  名称：

  Tandem cyclization-cycloaddition reaction of rhodium carbenoids. Studies dealing with the geometric requirements of dipole formation

  摘要：

  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.

  DOI：

  10.1021/jo00010a019

文献信息

• Studies dealing with the excited-state behavior of substituted 8-oxabicyclo[3.2.1]oct-6-en-2-ones
  作者：Albert Padwa、Lin Zhi、Glen E. Fryxell

  DOI：10.1021/jo00003a032

  日期：1991.2

  A series of 8-oxabicyclo [3.2.1]oct-6-en-2-ones was prepared by the rhodium(II)-catalyzed cyclization-cycloaddition reaction of alpha-diazopentanedione with various alkynes. The photochemical behavior of these oxabicyclic enones was investigated. Both direct and sensitized photolysis cleanly results in a 1,3-acyl shift. A slower, secondary photoprocess involving intramolecular hydrogen atom transfer and intramolecular cycloaddition of the resulting ketene was also uncovered. The photobehavior of the closely related 9-oxabenzocycloheptene system was also examined. The initially formed 1,3-sigmatropic rearranged product was found to undergo a novel 1,4-methoxyl migration on extended photolysis. The photochemistry of the homologous 7-oxabicyclo[2.2.1]hepten-2-one was studied. The results obtained can be interpreted in terms of an initial Norrish type I cleavage. The resulting diradical either couples to give the 1,3-acyl shift product or undergoes bond fragmentation, giving products derived from a stepwise retro-Diels-Alder reaction.
• PADWA, ALBERT;ZHI, LIN;FRYXELL, GLEN E., J. ORG. CHEM., 56,(1991) N, C. 1077-1083
  作者：PADWA, ALBERT、ZHI, LIN、FRYXELL, GLEN E.

  DOI：——

  日期：——
• 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.