(1S,2S)-cis-1-(3-chloropropyl)-2-ethylcyclopropanol | 1447152-11-5

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (1S,2S)-cis-1-(3-chloropropyl)-2-ethylcyclopropanol
• 英文别名: cis-1-(3-chloropropyl)-2-ethylcyclopropanol；(1S,2S)-1-(3-chloropropyl)-2-ethylcyclopropan-1-ol
• CAS: 1447152-11-5
• 化学式: C₈H₁₅ClO
• 分子量: 162.66
• InChiKey: GAAJNLJAPQZHHR-YUMQZZPRSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2
• 重原子数：
  10
• 可旋转键数：
  4
• 环数：
  1.0
• sp3杂化的碳原子比例：
  1.0
• 拓扑面积：
  20.2
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1S,2S)-cis-1-(3-chloropropyl)-2-ethylcyclopropanol 在 吡啶 、 magnesium(II) perchlorate 、 三乙胺 作用下， 以 乙醚 、 二氯甲烷 为溶剂， 生成 (E)-7-Chloro-4-methylene-hept-2-ene
  参考文献：
  名称：

  从 1,2-二取代环丙醇制备 2-取代 1,3-二烯烃的便捷立体选择性方法

  摘要：

  在二乙醚中的高氯酸镁和三乙胺的作用下，顺式-1,2-二取代环丙醇的磺酸盐以中等至良好的产率转化为2-取代的1,3-链二烯。在制备具有 1,2-二取代双键的链二烯时观察到高反式立体选择性。反应中的立体化学结果与协同反应机制一致，包括 Mg(ClO 4 ) 2 引发的环丙基磺酸盐的阳离子环丙基-烯丙基异构化，伴随着去质子化。

  DOI：

  10.1055/s-2003-44987
• 作为产物：
  描述：

  溴丁基-镁 、 4-氯丁酸乙酯 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56%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

文献信息

• Enantioselective cyclopropanation of carboxylic esters with alkyl magnesium bromides in the presence of titanium(IV) (4R,5R)-TADDOLates
  作者：Yulia A. Konik、Dzmitry G. Kananovich、Oleg G. Kulinkovich

  DOI：10.1016/j.tet.2013.05.118

  日期：2013.8

  The reaction of isopropyl 4-chlorobutyrate with 3 equiv of n-BuMgBr in the presence of 1 equiv of titanium(IV) (4R,5R)-TADDOLate in diethyl ether led to the formation of (1S,2S)-(3-chloropropyl)-2-ethylcyclopropanol in 55-70% yield and 55-65% ee. The reaction was performed in the presence of 20 mol % of the catalyst without significant loss in yield and enantioselectivity when solutions of the carboxylic ester and the Grignard reagent were added simultaneously at an equal rate to a refluxing solution of the titanium catalyst in ether. The cyclopropanation of isopropyl propionate under the same conditions gave (1S,2S)-1-ethyl-2-propylcyclopropanol in 50% yield and 65% ee. Its absolute configuration was determined by chemical correlation through acid-catalyzed isomerization to enantiomerically enriched (R)-(-)-4-methyl-3-heptanone, known as a minor component of the trail pheromone of ant Aphaenogaster albisetosus and enantiomer of the alarm pheromone of leaf-cutting ants Atta texana. (C) 2013 Elsevier Ltd. All rights reserved.