(2S)-ethyl-1-decanol

• 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: (2S)-ethyl-1-decanol
• 英文别名: (2S)-2-ethyldecan-1-ol
• 化学式: C₁₂H₂₆O
• 分子量: 186.338
• InChiKey: LTHQZRHTXDZWGX-LBPRGKRZSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  4.8
• 重原子数：
  13
• 可旋转键数：
  9
• 环数：
  0.0
• 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

• 作为产物：
  描述：

  正癸烯 、 三乙基铝 在 bis(1-(-)-neomenthylindenyl)zirconium dichloride 、 氧气 作用下， 以 二氯甲烷 为溶剂， 反应 50.0h， 以69%的产率得到
  参考文献：
  名称：

  Catalytic enantioselective ethylalumination of terminal alkenes: substrate effects and absolute configuration assignment

  摘要：

  The chemo- and enantioselectivity of the reaction of alkenes with AlEt3 catalyzed by bis(1-neomenthyl-indenyl)zirconium dichloride has been studied. The reaction with linear alkenes in a chlorinated solvent (CH2Cl2) gives mainly carbometallation products in 70-80% yield and with enantiomeric purity of 47-70%ee with an (S)-configuration. In the case of vinylcycloalkanes and styrene, the reaction provides roughly equal amounts of carbometallation products and substituted alumolanes with enantioselectivities of 39-69%ee and 40-57%ee, respectively.(R)-MTPA and (R)-2-phenylselenopropionic acid [(R)-PSPA] were used as the derivatization reagents for enantiomeric excess estimation and the absolute configuration assignment of beta-chiral primary alcohols and 2-substituted 1,4-butanediols resulting from oxidation and hydrolysis of the organoaluminum products. It was shown that the specific rotation changes sign in the series of enantiomerically enriched 2-ethyl-1-alkanols when going from beta-ethyl-substituted octanol to nonanol. The conformational analysis of the MTPA and PSPA esters of 2-ethyl-1-alkanols was performed and a dependence of their conformational composition on the type of substituent at the beta-stereogenic center was established. Calculation of the Se-77 NMR chemical shifts of the possible conformers of the PSPA esters demonstrated that the conformation of the selenium moiety has the most pronounced effect on the delta(Se) value. The high efficiency of PSPA application for the enantiomeric purity estimation and the absolute configuration assignment of 2-ethyl-1-alkanols is shown. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2014.11.019

文献信息

• Zirconium-Catalyzed Enantioselective Alkylalumination of Monosubstituted Alkenes Proceeding via Noncyclic Mechanism
  作者：Denis Y. Kondakov、Ei-ichi Negishi

  DOI：10.1021/ja953655m

  日期：1996.1.1
• Catalytic enantioselective ethylalumination of terminal alkenes: substrate effects and absolute configuration assignment
  作者：Lyudmila V. Parfenova、Pavel V. Kovyazin、Tatyana V. Tyumkina、Alyona V. Makrushina、Leonard M. Khalilov、Usein M. Dzhemilev

  DOI：10.1016/j.tetasy.2014.11.019

  日期：2015.2

  The chemo- and enantioselectivity of the reaction of alkenes with AlEt3 catalyzed by bis(1-neomenthyl-indenyl)zirconium dichloride has been studied. The reaction with linear alkenes in a chlorinated solvent (CH2Cl2) gives mainly carbometallation products in 70-80% yield and with enantiomeric purity of 47-70%ee with an (S)-configuration. In the case of vinylcycloalkanes and styrene, the reaction provides roughly equal amounts of carbometallation products and substituted alumolanes with enantioselectivities of 39-69%ee and 40-57%ee, respectively.(R)-MTPA and (R)-2-phenylselenopropionic acid [(R)-PSPA] were used as the derivatization reagents for enantiomeric excess estimation and the absolute configuration assignment of beta-chiral primary alcohols and 2-substituted 1,4-butanediols resulting from oxidation and hydrolysis of the organoaluminum products. It was shown that the specific rotation changes sign in the series of enantiomerically enriched 2-ethyl-1-alkanols when going from beta-ethyl-substituted octanol to nonanol. The conformational analysis of the MTPA and PSPA esters of 2-ethyl-1-alkanols was performed and a dependence of their conformational composition on the type of substituent at the beta-stereogenic center was established. Calculation of the Se-77 NMR chemical shifts of the possible conformers of the PSPA esters demonstrated that the conformation of the selenium moiety has the most pronounced effect on the delta(Se) value. The high efficiency of PSPA application for the enantiomeric purity estimation and the absolute configuration assignment of 2-ethyl-1-alkanols is shown. (C) 2014 Elsevier Ltd. All rights reserved.