1-deuterio-4-(2-methyl-1,3-dioxolan-2-yl)but-1-yne | 166907-60-4

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: 1-deuterio-4-(2-methyl-1,3-dioxolan-2-yl)but-1-yne
• 英文别名: 2-(4-Deuteriobut-3-ynyl)-2-methyl-1,3-dioxolane
• CAS: 166907-60-4
• 化学式: C₈H₁₂O₂
• 分子量: 141.174
• InChiKey: KVBBYSGYWFFEQS-MICDWDOJSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  1
• 重原子数：
  10
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.75
• 拓扑面积：
  18.5
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  叔丁基氯化镁 、 1-deuterio-4-(2-methyl-1,3-dioxolan-2-yl)but-1-yne 在 氯化铵 、 copper(I) bromide 、 lithium bromide 作用下， 生成 2-[(E)-3-deuterio-5,5-dimethylhex-3-enyl]-2-methyl-1,3-dioxolane 、 (E)-3-(deuteriomethylene)-2,2-dimethyl-5-(2-methyl-1,3-dioxolan-2-yl)pentane
  参考文献：
  名称：

  Mechanism of the Diastereoselective, Boron Trifluoride-Catalyzed Cyclization of Olefinic Tosylhydrazones to Stereolabeled, Bridgehead-Substituted Azoalkanes

  摘要：

  For the first time 1,4-dialkylated 2,3-diazabicyclo[2.2.1]hept-2-enes (5a-c) with stereolabels at the C-7 position have been prepared via the intramolecular cyclization of stereolabeled gamma,delta-unsaturated tosylhydrazones under acidic conditions. The stereochemically labeled olefinic carbonyl compounds 3, required for the preparation of the tosylhydrazones 4, were made by syn carbometalation of the appropriate terminal alkynes 1a,b(D) with dialkylcuprates in THF at 0 degrees C. Hydrolysis of the ketal functionality in the resulting linear alkenes 2 afforded the desired ketones 3. Although the boron trifluoride-catalyzed cyclization of the tosylhydrazones 4 led in all cases to mixtures of stereochemically labeled azoalkanes, the process is highly diastereoselective in that the initial syn/anti diastereomeric ratio of the tosylhydrazones 4 dictates the stereochemistry of the final azoalkanes 5. Thus, in the deuterium-labeled substrates, the syn tosylhydrazone of (E)-4a(D) affords the azoalkane syn-5a(D) through the orthogonal syn-A arrangement of the tosylhydrazone and olefin functionalities, while the anti tosylhydrazone of (E)-4a(D) leads to the azoalkane anti-5a(D) through the parallel anti-B arrangement, irrespective of the stereolabeled olefin geometry. A delicate balance of steric effects in the orthogonal and parallel conformers for the syn and anti diastereomers of the tosylhydrazones seems to control the observed diastereoselectivity.

  DOI：

  10.1021/ja00111a005
• 作为产物：
  描述：

  2-(but-3'-ynyl)-2-methyl-1,3-dioxolane 在 乙基溴化镁 、 重水 作用下， 生成 1-deuterio-4-(2-methyl-1,3-dioxolan-2-yl)but-1-yne
  参考文献：
  名称：

  Mechanism of the Diastereoselective, Boron Trifluoride-Catalyzed Cyclization of Olefinic Tosylhydrazones to Stereolabeled, Bridgehead-Substituted Azoalkanes

  摘要：

  For the first time 1,4-dialkylated 2,3-diazabicyclo[2.2.1]hept-2-enes (5a-c) with stereolabels at the C-7 position have been prepared via the intramolecular cyclization of stereolabeled gamma,delta-unsaturated tosylhydrazones under acidic conditions. The stereochemically labeled olefinic carbonyl compounds 3, required for the preparation of the tosylhydrazones 4, were made by syn carbometalation of the appropriate terminal alkynes 1a,b(D) with dialkylcuprates in THF at 0 degrees C. Hydrolysis of the ketal functionality in the resulting linear alkenes 2 afforded the desired ketones 3. Although the boron trifluoride-catalyzed cyclization of the tosylhydrazones 4 led in all cases to mixtures of stereochemically labeled azoalkanes, the process is highly diastereoselective in that the initial syn/anti diastereomeric ratio of the tosylhydrazones 4 dictates the stereochemistry of the final azoalkanes 5. Thus, in the deuterium-labeled substrates, the syn tosylhydrazone of (E)-4a(D) affords the azoalkane syn-5a(D) through the orthogonal syn-A arrangement of the tosylhydrazone and olefin functionalities, while the anti tosylhydrazone of (E)-4a(D) leads to the azoalkane anti-5a(D) through the parallel anti-B arrangement, irrespective of the stereolabeled olefin geometry. A delicate balance of steric effects in the orthogonal and parallel conformers for the syn and anti diastereomers of the tosylhydrazones seems to control the observed diastereoselectivity.

  DOI：

  10.1021/ja00111a005

文献信息

• Mechanism of the Diastereoselective, Boron Trifluoride-Catalyzed Cyclization of Olefinic Tosylhydrazones to Stereolabeled, Bridgehead-Substituted Azoalkanes
  作者：Waldemar Adam、Coskun Sahin、Martin Schneider

  DOI：10.1021/ja00111a005

  日期：1995.2

  For the first time 1,4-dialkylated 2,3-diazabicyclo[2.2.1]hept-2-enes (5a-c) with stereolabels at the C-7 position have been prepared via the intramolecular cyclization of stereolabeled gamma,delta-unsaturated tosylhydrazones under acidic conditions. The stereochemically labeled olefinic carbonyl compounds 3, required for the preparation of the tosylhydrazones 4, were made by syn carbometalation of the appropriate terminal alkynes 1a,b(D) with dialkylcuprates in THF at 0 degrees C. Hydrolysis of the ketal functionality in the resulting linear alkenes 2 afforded the desired ketones 3. Although the boron trifluoride-catalyzed cyclization of the tosylhydrazones 4 led in all cases to mixtures of stereochemically labeled azoalkanes, the process is highly diastereoselective in that the initial syn/anti diastereomeric ratio of the tosylhydrazones 4 dictates the stereochemistry of the final azoalkanes 5. Thus, in the deuterium-labeled substrates, the syn tosylhydrazone of (E)-4a(D) affords the azoalkane syn-5a(D) through the orthogonal syn-A arrangement of the tosylhydrazone and olefin functionalities, while the anti tosylhydrazone of (E)-4a(D) leads to the azoalkane anti-5a(D) through the parallel anti-B arrangement, irrespective of the stereolabeled olefin geometry. A delicate balance of steric effects in the orthogonal and parallel conformers for the syn and anti diastereomers of the tosylhydrazones seems to control the observed diastereoselectivity.