5-acetamido-3,3a,4,5,6,6a-hexahydro<3β,3aα,5α,6β,6aα>-3,6-methano-2H-cyclopentafuran-2-one | 135225-28-4

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 内酯类
• 英文名称: 5-acetamido-3,3a,4,5,6,6a-hexahydro<3β,3aα,5α,6β,6aα>-3,6-methano-2H-cyclopentafuran-2-one
• 英文别名: [(1R,3R,7S,9R)-4-oxo-5-oxatricyclo[4.3.0.03,7]nonan-9-yl] carbamate
• CAS: 135225-28-4
• 化学式: C₉H₁₁NO₄
• 分子量: 197.191
• InChiKey: LFXIKUVJGJDZJI-HZYAIORGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.1
• 重原子数：
  14
• 可旋转键数：
  2
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.78
• 拓扑面积：
  78.6
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  endo-norbornenecarboxylic acid 、 乙腈 在 碘苯二乙酸 作用下， 反应 72.0h， 以18%的产率得到5-acetamido-3,3a,4,5,6,6a-hexahydro<3β,3aα,5α,6β,6aα>-3,6-methano-2H-cyclopentafuran-2-one
  参考文献：
  名称：

  Lewis acidic catalysts for olefin epoxidation by iodosylbenzene

  摘要：

  A ferric complex, (Et3HN)Fe(III)(bpb)Cl2, has been synthesized, and its structure has been determined by X-ray crystallography. This complex and its triflate derivative, (Et3HN)Fe(III)(bpb)(OTf)2, are found to catalyze the epoxidation of a variety of olefins by iodosylbenzene, OIPh. These reactions give little allylic oxidation of cyclohexene and stereochemical retention with cis-stilbene. Al(OTf)3, a nonredox metal salt, has also been found to catalyze the epoxidation of cyclohexene by iodosylbenzene, and the reactivity is quite similar to that of Fe(OTf)3, which we studied previously. In addition to epoxides, other products were observed. For the reactions containing Fe(OTf)3, Al(OTf)3, or (Et3HN)Fe(III)(bpb)(OTf)2, cis-1,2-cyclohexanediol ditriflate and 3-acetamidocyclohexene were found. The amide oxygen in 3-acetamidocyclohexene was derived from iodosylbenzene as verified by isotopic labeling using (OIPh)-O-18. For the reactions containing (Et3HN)Fe(III)(bpb)Cl2, FeCl3, or AlCl3, trans-1,2-dichlorocyclohexane and 3-chlorocyclohexene were observed. 1,4-Diiodobenzene was found in all of the reactions. The presence of these products suggests strongly that the mechanisms of these reactions are related to those occurring between soluble iodine(III)-containing compounds and olefins in the absence of any metal catalysts. A new mechanism that accounts for all of the products is proposed which involves electrophilic attack on the olefin by the iodine(III) center in a metal-iodosylbenzene complex. The reactions of PhI(OAc)2 with norbornenecarboxylic acid or norbornene in different solvents were also investigated. The products isolated were shown to be 5-(acetyloxy)-3,3a,4,5,6,6a-hexahydro[3-beta,3a-alpha,5-alpha,6-beta,6a-alpha]-3,6-methano-2H-cyclopenta[b]furan-2-one (1), 5-acetamido-3,3a,4,5,6,6a-hexahydro[3-beta,3a-alpha,5-alpha,6-beta,6a-alpha]-3,6-methano-2H-cyclopenta[b]furan-2-one (2), and exo-2-acetoxy-syn-7-acetamidonorbornane (3). The structures of 1 and 3 were determined by X-ray crystallography. The formation of these products provides additional evidence for the electrophilic character of iodine(III) compounds.

  DOI：

  10.1021/ja00019a016