(S)-2-(2-diazo-2-phenylacetoxy)propionic acid ethyl ester | 873108-52-2

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (S)-2-(2-diazo-2-phenylacetoxy)propionic acid ethyl ester
• 英文别名: ethyl (2S)-2-(2-diazo-2-phenylacetyl)oxypropanoate
• CAS: 873108-52-2
• 化学式: C₁₃H₁₄N₂O₄
• 分子量: 262.265
• InChiKey: PLGWSQAHGZUUNW-VIFPVBQESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.7
• 重原子数：
  19
• 可旋转键数：
  7
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.31
• 拓扑面积：
  54.6
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  (S)-2-(2-diazo-2-phenylacetoxy)propionic acid ethyl ester 、 tert-butyl 3-(((tert-butyldimethylsilyl)oxy)methyl)-1H-indole-1-carboxylate 在 辛酸铑 作用下， 以 various solvent(s) 为溶剂， 反应 1.0h， 以42%的产率得到tert-butyl 3-(1-(tert-butyldimethylsilyloxy)-3-((S)-1-ethoxy-1-oxopropan-2-yloxy)-3-oxo-2-phenylpropyl)-1H-indole-1-carboxylate
  参考文献：
  名称：

  Investigation into Factors Influencing Stereoselectivity in the Reactions of Heterocycles with Donor−Acceptor-Substituted Rhodium Carbenoids

  摘要：

  Rhodium-catalyzed decomposition of aryldiazoacetates in the presence of pyrroles or furans results in mono- or biscyclopropanation of the heterocycle, but with opposite enantioinduction. In the absence of sterically encumbering groups, the cyclopropanation of furan occurs with initial bond formation at the 2-position. If this pathway is sterically blocked, cyclopropanation can occur with initial bond formation at the 3-position of the furan ring; in this case, the cyclopropanation reaction takes place on the opposite face of the heterocycle, and the opposite enantioinduction is observed. Upon extension of this methodology to benzofurans, a highly enantioselective monocyclopropanation reaction occurs to furnish a product derived from initial bond formation at the 2-position of the benzofuran. When this reaction pathway is inhibited by sterically encumbering substituents on the benzofuran, no cyclopropanation of the furan ring is observed, and instead, double cyclopropanation of the benzene ring occurs. Double cyclopropanation of the benzene ring was also observed in reactions with indoles.

  DOI：

  10.1021/jo060779g
• 作为产物：
  描述：

  (S)-2-Phenylacetoxypropionsaeureethylester 在 4-乙酰氨基苯磺酰叠氮 、 1,8-二氮杂双环[5.4.0]十一碳-7-烯 作用下， 以 乙腈 为溶剂， 反应 12.0h， 以89%的产率得到(S)-2-(2-diazo-2-phenylacetoxy)propionic acid ethyl ester
  参考文献：
  名称：

  Asymmetric Intermolecular C−H Functionalization of Benzyl Silyl Ethers Mediated by Chiral Auxiliary-Based Aryldiazoacetates and Chiral Dirhodium Catalysts

  摘要：

  C-H functionalization of benzyl silyl ethers by means of rhodium-catalyzed insertions of aryldiazoacetates can be achieved in a highly diastereoselective and enantioselective manner by judicious choice of chiral catalyst or auxiliary. The dirhodium tetraprolinates such as Rh-2((S)-DOSP)(4) have been widely successful as chiral catalysts in the C-H functionalization chemistry of aryldiazoacetates, but give poor enantioselectivity in the reactions of aryldiazoacetates with benzyl silyl ether derivatives. The use of (S)-lactate as a chiral auxiliary resulted in C-H functionalization with moderately high diastereoselectivity (79-88% de) and enantioselectivity (68-85% ee). The best results (91-95% de, 95-98% ee), however, were achieved using Hashimoto's Rh-2((S)-PTTL)(4) catalyst.

  DOI：

  10.1021/jo051747g

文献信息

• Investigation into Factors Influencing Stereoselectivity in the Reactions of Heterocycles with Donor−Acceptor-Substituted Rhodium Carbenoids
  作者：Simon J. Hedley、Dominic L. Ventura、Paulina M. Dominiak、Cara L. Nygren、Huw M. L. Davies

  DOI：10.1021/jo060779g

  日期：2006.7.1

  Rhodium-catalyzed decomposition of aryldiazoacetates in the presence of pyrroles or furans results in mono- or biscyclopropanation of the heterocycle, but with opposite enantioinduction. In the absence of sterically encumbering groups, the cyclopropanation of furan occurs with initial bond formation at the 2-position. If this pathway is sterically blocked, cyclopropanation can occur with initial bond formation at the 3-position of the furan ring; in this case, the cyclopropanation reaction takes place on the opposite face of the heterocycle, and the opposite enantioinduction is observed. Upon extension of this methodology to benzofurans, a highly enantioselective monocyclopropanation reaction occurs to furnish a product derived from initial bond formation at the 2-position of the benzofuran. When this reaction pathway is inhibited by sterically encumbering substituents on the benzofuran, no cyclopropanation of the furan ring is observed, and instead, double cyclopropanation of the benzene ring occurs. Double cyclopropanation of the benzene ring was also observed in reactions with indoles.
• Asymmetric Intermolecular C−H Functionalization of Benzyl Silyl Ethers Mediated by Chiral Auxiliary-Based Aryldiazoacetates and Chiral Dirhodium Catalysts
  作者：Huw M. L. Davies、Simon J. Hedley、Brooks R. Bohall

  DOI：10.1021/jo051747g

  日期：2005.12.1

  C-H functionalization of benzyl silyl ethers by means of rhodium-catalyzed insertions of aryldiazoacetates can be achieved in a highly diastereoselective and enantioselective manner by judicious choice of chiral catalyst or auxiliary. The dirhodium tetraprolinates such as Rh-2((S)-DOSP)(4) have been widely successful as chiral catalysts in the C-H functionalization chemistry of aryldiazoacetates, but give poor enantioselectivity in the reactions of aryldiazoacetates with benzyl silyl ether derivatives. The use of (S)-lactate as a chiral auxiliary resulted in C-H functionalization with moderately high diastereoselectivity (79-88% de) and enantioselectivity (68-85% ee). The best results (91-95% de, 95-98% ee), however, were achieved using Hashimoto's Rh-2((S)-PTTL)(4) catalyst.