(1R*,4S*,5S*,2'R*)-7,7-dimethoxy-1,2,3,4-tetrachloro-5-<2'-(2'-amino-1'-hydroxy)-propyl>-bicyclo<2.2.1>hept-2-ene | 130747-96-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1R*,4S*,5S*,2'R*)-7,7-dimethoxy-1,2,3,4-tetrachloro-5-<2'-(2'-amino-1'-hydroxy)-propyl>-bicyclo<2.2.1>hept-2-ene
• 英文别名: (2R)-2-amino-2-[(1S,2S,4R)-1,4,5,6-tetrachloro-7,7-dimethoxy-2-bicyclo[2.2.1]hept-5-enyl]propan-1-ol
• CAS: 130747-96-5；130844-92-7
• 化学式: C₁₂H₁₇Cl₄NO₃
• 分子量: 365.084
• InChiKey: IWCZDFKHUQMQMZ-WBAWJMECSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  0.7
• 重原子数：
  20
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.83
• 拓扑面积：
  64.7
• 氢给体数：
  2
• 氢受体数：
  4

反应信息

• 作为反应物：
  描述：

  (1R*,4S*,5S*,2'R*)-7,7-dimethoxy-1,2,3,4-tetrachloro-5-<2'-(2'-amino-1'-hydroxy)-propyl>-bicyclo<2.2.1>hept-2-ene 在 氨 、 lithium 作用下， 以 乙醚 、 乙醇 为溶剂， 反应 0.17h， 以85%的产率得到<(+/-)-(1S,4S,5S)>-7,7-Dimethoxy-5-<(S)-1'-amino-2'-hydroxy-1'-methylethyl>bicyclo<2.2.1>hept-2-ene
  参考文献：
  名称：

  An Efficient Dechlorination Method for 1,2,3,4-Tetrachloro-5,5-dimethoxycyclopentadiene Diels-Alder Adducts: Inverse Addition-Ethereal Birch Reduction Conditions

  摘要：

  本研究描述了用于 1,2,3,4- 四氯-5,5-二甲氧基环戊二烯 Diels-Alder 加合物选择性脱氯的改良 Birch 还原条件。在 - 78°C 温度下，将液氨中的锂悬浮液反向加入加合物的稀乙醇溶液中，可实现无伴随烯还原的清洁脱氯。

  DOI：

  10.1055/s-1990-26968
• 作为产物：
  描述：

  (+/-)-N-benzoyl-α-vinylalanine methyl ester 在 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 硫酸 作用下， 以 甲醇 、 乙醚 、 乙醇 、 水 为溶剂， 反应 83.5h， 生成 (1R*,4S*,5S*,2'R*)-7,7-dimethoxy-1,2,3,4-tetrachloro-5-<2'-(2'-amino-1'-hydroxy)-propyl>-bicyclo<2.2.1>hept-2-ene
  参考文献：
  名称：

  A new retro-aza-ene reaction: formal reductive amination of an α-keto acid to an α-amino acid

  摘要：

  Two diastereomeric reductive amination reagents, 1a and 1b, were synthesized. Each reagent was condensed with ethyl pyruvate as a model alpha-keto acid. Flash vacuum pyrolysis of the pyruvate adducts, 10a and 10b, results in cheleotropic elimination of CO, followed by a new type of retro-aza-ene reaction. A molecule of benzene and a protected alanine derivative, 11, are produced in the retro-ene reaction. This sequence constitutes the first formal reductive amination of an alpha-keto acid via a thermal rearrangement. Diastereomer 10b undergoes the rearrangement more readily than diastereomer 10a, indicating that an exo transition state is preferred over an endo transition state for this particular retro-aza-ene reaction.

  DOI：

  10.1016/s0040-4020(01)88730-5

文献信息

• A new retro-aza-ene reaction: formal reductive amination of an α-keto acid to an α-amino acid
  作者：David B. Berkowitz、W. Bernd Schweizer

  DOI：10.1016/s0040-4020(01)88730-5

  日期：1992.2

  Two diastereomeric reductive amination reagents, 1a and 1b, were synthesized. Each reagent was condensed with ethyl pyruvate as a model alpha-keto acid. Flash vacuum pyrolysis of the pyruvate adducts, 10a and 10b, results in cheleotropic elimination of CO, followed by a new type of retro-aza-ene reaction. A molecule of benzene and a protected alanine derivative, 11, are produced in the retro-ene reaction. This sequence constitutes the first formal reductive amination of an alpha-keto acid via a thermal rearrangement. Diastereomer 10b undergoes the rearrangement more readily than diastereomer 10a, indicating that an exo transition state is preferred over an endo transition state for this particular retro-aza-ene reaction.
• An Efficient Dechlorination Method for 1,2,3,4-Tetrachloro-5,5-dimethoxycyclopentadiene Diels-Alder Adducts: Inverse Addition-Ethereal Birch Reduction Conditions
  作者：David B. Berkowitz

  DOI：10.1055/s-1990-26968

  日期：——

  Modified Birch reduction conditions for the selective dechlorination of 1,2,3,4-tetrachloro-5,5-dimethoxycyclopentadiene Diels-Alder adducts are described. Inverse addition of a suspension of lithium in liquid ammonia to a dilute ethereal solution of the adduct at - 78°C gives clean dechlorination with no accompanying alkene reduction.

  本研究描述了用于 1,2,3,4- 四氯-5,5-二甲氧基环戊二烯 Diels-Alder 加合物选择性脱氯的改良 Birch 还原条件。在 - 78°C 温度下，将液氨中的锂悬浮液反向加入加合物的稀乙醇溶液中，可实现无伴随烯还原的清洁脱氯。