benzyl (3S,9S)-2,8-dioxo-1,7-diazatricyclo[7.3.0.03,7]dodecane-3-carboxylate | 454693-93-7

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: benzyl (3S,9S)-2,8-dioxo-1,7-diazatricyclo[7.3.0.03,7]dodecane-3-carboxylate
• CAS: 454693-93-7
• 化学式: C₁₈H₂₀N₂O₄
• 分子量: 328.368
• InChiKey: NJCLDHOYHMCBRI-KSSFIOAISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  66.9
• 氢给体数：
  0
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  benzyl (3S,9S)-2,8-dioxo-1,7-diazatricyclo[7.3.0.03,7]dodecane-3-carboxylate 在 双(三甲基硅烷基)氨基钾 、 Tris-N₃ 、 potassium acetate 作用下， 以 四氢呋喃 、 水 为溶剂， 生成 benzyl (3S,9R)-9-azido-2,8-dioxo-1,7-diazatricyclo[7.3.0.03,7]dodecane-3-carboxylate
  参考文献：
  名称：

  Highly Diastereoselective Desymmetrizations of Cyclo(Pro,Pro):  An Enantioselective Strategy toward Phakellstatin and Phakellin

  摘要：

  [GRAPHICS]Monoenolates of C-2-symmetric, proline-derived piperazine-2,5-diones were generated and trapped with a variety of electrophiles to produce, in a highly diastereoselective fashion, functionalized diketopiperazines (DKPs). These reactions provide the basis for an asymmetric, desymmetrization strategy toward the marine alkaloids phakellstatin and phakellin, The relative stereochemistry of the functionalized DKPs was confirmed by single-crystal X-ray analysis and/or NOE experiments. Bis-functionalization of the DKPs was also found to proceed with high levels of diastereoselectivity.

  DOI：

  10.1021/ol026140q
• 作为产物：
  描述：

  氯甲酸苄酯 、 维格列汀杂质 在 双(三甲基硅烷基)氨基钾 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 7.5h， 以70%的产率得到benzyl (3S,9S)-2,8-dioxo-1,7-diazatricyclo[7.3.0.03,7]dodecane-3-carboxylate
  参考文献：
  名称：

  Highly Diastereoselective Desymmetrizations of Cyclo(Pro,Pro):  An Enantioselective Strategy toward Phakellstatin and Phakellin

  摘要：

  [GRAPHICS]Monoenolates of C-2-symmetric, proline-derived piperazine-2,5-diones were generated and trapped with a variety of electrophiles to produce, in a highly diastereoselective fashion, functionalized diketopiperazines (DKPs). These reactions provide the basis for an asymmetric, desymmetrization strategy toward the marine alkaloids phakellstatin and phakellin, The relative stereochemistry of the functionalized DKPs was confirmed by single-crystal X-ray analysis and/or NOE experiments. Bis-functionalization of the DKPs was also found to proceed with high levels of diastereoselectivity.

  DOI：

  10.1021/ol026140q

文献信息

• Enantioselective Total Synthesis of (+)-Dibromophakellstatin
  作者：Karine G. Poullennec、Daniel Romo

  DOI：10.1021/ja034575i

  日期：2003.5.1

  The first enantioselective total synthesis of (+)-phakellstatin and (+)-dibromophakellstatin was achieved. Key steps in the synthesis were a desymmetrization of the diketopiperazine (S,S)-cyclo (Pro, Pro) via a diastereoselective acylation, an intramolecular Mitsunobu reaction to introduce the C6 aminal, and a tandem Hofmann rearrangement/cyclization to simultaneously introduce the C10 quaternary aminal

  实现了 (+)-phakellstatin 和 (+)-dibromophakellstatin 的第一个对映选择性全合成。合成的关键步骤是通过非对映选择性酰化使二酮哌嗪 (S,S)-环 (Pro, Pro) 去对称化，通过分子内 Mitsunobu 反应引入 C6 氨基，以及串联霍夫曼重排/环化同时引入 C10四元胺中心并输送环脲。该合成还证明了吡咯并缩醛胺的异常稳定性。重要的是，该策略有可能生产生物研究所需的衍生自 (R,R)-环 (Pro, Pro) 的 phakellstatin 衍生物。预计类似的环化协议也适用于 palau'amine 的合成。