1,1,1,3,3,3-hexafluoropropan-2-yl 4-chlorobutanoate

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 脂肪酰基
• 英文名称: 1,1,1,3,3,3-hexafluoropropan-2-yl 4-chlorobutanoate
• 英文别名: 1,1,1,3,3,3-Hexafluoropropan-2-yl 4-chlorobutanoate
• 化学式: C₇H₇ClF₆O₂
• 分子量: 272.575
• InChiKey: RPCNLUUBNUAMRF-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.3
• 重原子数：
  16
• 可旋转键数：
  5
• 环数：
  0.0
• sp3杂化的碳原子比例：
  0.86
• 拓扑面积：
  26.3
• 氢给体数：
  0
• 氢受体数：
  8

反应信息

• 作为反应物：
  描述：

  1,1,1,3,3,3-hexafluoropropan-2-yl 4-chlorobutanoate 、 magnesium,2-methylbutane,bromide 在 [(4R,5R)-2,2-dimethyl-α,α,α',α'-tetraphenyl-1,3-dioxolane-4,5-dimethanolato-O,O']diisopropoxytitanium(IV) 、 水 作用下， 以 乙醚 、 甲苯 为溶剂， 反应 0.67h， 以84%的产率得到
  参考文献：
  名称：

  对烷基钛复杂化合物转化的机理和立体化学的认识。钛环丙烷试剂在羧酸酯环丙烷化中的增强对映选择性

  摘要：

  AbstractThe dependence of the stereoselectivity of the cyclopropanation reaction of γ,γ‐diphenyl‐γ‐butyrolactone and carboxylic esters with alkylmagnesium bromides in the presence of titanium(IV) TADDOLates on the structure of the reactants has been examined in detail. It has been found that the enantioselectivity in the formation of cis‐1,2‐disubstituted cyclopropanols is a function of the structure of the carboxylic ester alkoxy group and leads, in the case of cyclopropanation of hexafluoroisopropyl alkanoates, to 84% ee. To rationalize these observations, as well as the NMR data on the structures of the TADDOL‐derived alkyltitanium species, a new mechanistic model for the formation of the five‐coordinated chiral titanacyclopropane reactive intermediates and their subsequent reorganization in the reactions with esters is proposed. The essential features of this model consist in the generation of configurationally stable TADDOL derived titanacyclopropane species with an apical or equatorial position of the stereogenic carbanion center which is followed by retention or inversion of absolute configuration in course of the displacement of the carboxylic ester alkoxy group.magnified image

  DOI：

  10.1002/adsc.201400480
• 作为产物：
  描述：

  六氟异丙醇 、 4-氯丁酰氯 在 吡啶 作用下， 以 二氯甲烷 为溶剂， 反应 3.0h， 以90%的产率得到1,1,1,3,3,3-hexafluoropropan-2-yl 4-chlorobutanoate
  参考文献：
  名称：

  对烷基钛复杂化合物转化的机理和立体化学的认识。钛环丙烷试剂在羧酸酯环丙烷化中的增强对映选择性

  摘要：

  AbstractThe dependence of the stereoselectivity of the cyclopropanation reaction of γ,γ‐diphenyl‐γ‐butyrolactone and carboxylic esters with alkylmagnesium bromides in the presence of titanium(IV) TADDOLates on the structure of the reactants has been examined in detail. It has been found that the enantioselectivity in the formation of cis‐1,2‐disubstituted cyclopropanols is a function of the structure of the carboxylic ester alkoxy group and leads, in the case of cyclopropanation of hexafluoroisopropyl alkanoates, to 84% ee. To rationalize these observations, as well as the NMR data on the structures of the TADDOL‐derived alkyltitanium species, a new mechanistic model for the formation of the five‐coordinated chiral titanacyclopropane reactive intermediates and their subsequent reorganization in the reactions with esters is proposed. The essential features of this model consist in the generation of configurationally stable TADDOL derived titanacyclopropane species with an apical or equatorial position of the stereogenic carbanion center which is followed by retention or inversion of absolute configuration in course of the displacement of the carboxylic ester alkoxy group.magnified image

  DOI：

  10.1002/adsc.201400480

文献信息

• Insight into the Mechanism and Stereochemistry of the Transformations of Alkyltitanium Ate-Complexes. An Enhanced Enantioselectivity in the Cyclopropanation of the Carboxylic Esters with Titanacyclopropane Reagents
  作者：Oleg G. Kulinkovich、Dzmitry G. Kananovich、Margus Lopp、Victor Snieckus

  DOI：10.1002/adsc.201400480

  日期：2014.11.24

  AbstractThe dependence of the stereoselectivity of the cyclopropanation reaction of γ,γ‐diphenyl‐γ‐butyrolactone and carboxylic esters with alkylmagnesium bromides in the presence of titanium(IV) TADDOLates on the structure of the reactants has been examined in detail. It has been found that the enantioselectivity in the formation of cis‐1,2‐disubstituted cyclopropanols is a function of the structure of the carboxylic ester alkoxy group and leads, in the case of cyclopropanation of hexafluoroisopropyl alkanoates, to 84% ee. To rationalize these observations, as well as the NMR data on the structures of the TADDOL‐derived alkyltitanium species, a new mechanistic model for the formation of the five‐coordinated chiral titanacyclopropane reactive intermediates and their subsequent reorganization in the reactions with esters is proposed. The essential features of this model consist in the generation of configurationally stable TADDOL derived titanacyclopropane species with an apical or equatorial position of the stereogenic carbanion center which is followed by retention or inversion of absolute configuration in course of the displacement of the carboxylic ester alkoxy group.magnified image