[1Z,2(1S,2S)]-2-(2-vinylcyclopentyl)ethenyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 唑烷类
• 英文名称: [1Z,2(1S,2S)]-2-(2-vinylcyclopentyl)ethenyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
• 英文别名: [(Z)-2-[(1S,2S)-2-ethenylcyclopentyl]ethenyl] 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
• 化学式: C₁₇H₂₇NO₃
• 分子量: 293.406
• InChiKey: HZXSLHWXPAMXSW-MCZKDORBSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  21
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.71
• 拓扑面积：
  38.8
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  戊二醛 在 甲醇 、 正丁基锂 、 水 、 sodium hydride 、 二异丁基氢化铝 、 potassium carbonate 、 甲基磺酰氯 、 lithium chloride 、 鹰爪豆碱 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 生成 [1Z,2(1S,2S)]-2-(2-vinylcyclopentyl)ethenyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
  参考文献：
  名称：

  Chiral Induction by Elimination‐Coupled Lithium–Ene Reaction: Synthesis of (+)‐(3 R ,4 R )‐1,2‐Dihydromultifidene

  摘要：

  Cyclization of the alkadienyl carbamates 1 to the cis-divinylcyclopentanes 2 with high enantioselectivity and diastereoselectivity has been successfully achieved by (-)-sparteine-induced asymmetric deprotonation. The conversion may be described as a hybrid of a lithium-ene reaction and an Sn ' reaction.

  DOI：

  10.1002/(sici)1521-3773(19990215)38:4<546::aid-anie546>3.0.co;2-#

文献信息

• Asymmetric Synthesis of <i>cis</i>-1,2-Dialkenyl-Substituted Cyclopentanes via (−)-Sparteine-Mediated Lithiation and Cycloalkylation of a 9-Chloro-2,7-nonadienyl Carbamate
  作者：Alexander Deiters、Dieter Hoppe

  DOI：10.1021/jo015548i

  日期：2001.4.1

  Herein we report our comprehensive results in enantioselective cyclopentane synthesis via stereogenic allyllithium compounds. The described cycloalkylation reaction starts with a (-)-sparteine-mediated asymmetric deprotonation of the 2,7-alkadienyl carbamate 7e and leads to the enantioenriched (80% ee) and diastereomerically pure (dr = 99:1) cis-1,2-divinyl-cyclopentane 8, by a subsequent cyclization

  本文中，我们报告了通过立体异构烯丙基锂化合物合成对映选择性环戊烷的综合结果。所述的环烷基化反应始于2,7-链二烯基氨基甲酸酯7e的（-）-天冬氨酸介导的不对称脱质子反应，并导致对映体富集（80％ee）和非对映体纯（dr = 99：1）顺式1,2 -二乙烯基环戊烷8，随后环化并消除氯化锂。该反应机理已经通过甲硅烷基化和硫代去锡烷基化实验进行了研究，并被发现代表了一个完全区域选择性的抗S（N）'S（E）'反应。在保持双键构型的情况下用各种亲电试剂捕获乙烯基锂中间体12扩大了该环化的应用领域。
• Planar-Chiral (2E,7Z)- and (2Z,7E)-Cyclonona-2,7-dien-1-yl Carbamates by Asymmetric, Bis-Allylic α,α′-Cycloalkylation—Studies on Their Conformational Stability
  作者：Alexander Deiters、Christian Mück-Lichtenfeld、Roland Fröhlich、Dieter Hoppe

  DOI：10.1002/1521-3765(20020415)8:8<1833::aid-chem1833>3.0.co;2-c

  日期：2002.4.15

  Enantiomerically enriched (> 80% ee) (M,1R,2Z,7E)- and (M,1R,2E,7Z)-cyclonona-2,7-dienyl carbamates have been synthesized by an intramolecular cycloalkylation of the corresponding 1-lithio-9-chloronona-2,7-dienyl carbamates. The enantioen-riched precursors were generated by asymmetric deprotonation of the dienyl carbamates by means of n-BuLi/(-)-sparteine. The primarily obtained cyclononadienes, each bearing one element of planar and centre chirality, were formed by an alpha,alpha' coupling of both allylic moieties. These are the thermodynamically less favoured epimers. which arise from those allyllithiums bearing the carbamoyloxy residue in a 1-endo position. Both (M,R)-cyclononadienes epimerize slowly (t(1/2) = 209 min and 328 min at 308 K) with inversion of the planar chirality to the corresponding, more stable (P)-epimers (ratios 3:97 and 30:70). The kinetics were measured by H-1 NMR spectroscopy, the activation energies E-A were found to be 26.4 and 27.5 kcal mol(-1). From quantum-chemical calculations with the B3LYP density functional, the epimerization process was shown to consist of two coupled major conformational changes with high energy barriers. The calculated values match well with the observed ones.