(2Z,7E)-9-chloronona-2,7-dienyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate | 294678-31-2

• 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: (2Z,7E)-9-chloronona-2,7-dienyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
• 英文别名: (2Z,7E)-9-chloro-2,7-nonadienyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate；[(2Z,7E)-9-chloronona-2,7-dienyl] 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
• CAS: 294678-31-2
• 化学式: C₁₇H₂₈ClNO₃
• 分子量: 329.867
• InChiKey: POIYUSKCMMVOKE-GOOGBFEESA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.8
• 重原子数：
  22
• 可旋转键数：
  8
• 环数：
  1.0
• 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

• 作为反应物：
  描述：

  (2Z,7E)-9-chloronona-2,7-dienyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate 在 正丁基锂 、 四甲基乙二胺 作用下， 以 正己烷 、 甲苯 为溶剂， 生成 rac-(M,1R,2Z,7E)-cyclonona-2,7-dien-1-yl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate 、 rac-(P,1R,2Z,7E)-cyclonona-2,7-dien-1-yl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

  10.1002/1521-3765(20020415)8:8<1833::aid-chem1833>3.0.co;2-c
• 作为产物：
  描述：

  2,2,4,4-tetramethyl-1,3-oxazolidine-3-carbonyl chloride 在 正丁基锂 、 sodium hydride 、 二异丁基氢化铝 、 pyridinium chlorochromate 、 lithium chloride 作用下， 以 四氢呋喃 、 正己烷 、 正庚烷 、 二氯甲烷 为溶剂， 反应 52.92h， 生成 (2Z,7E)-9-chloronona-2,7-dienyl 2,2,4,4-tetramethyl-1,3-oxazolidine-3-carboxylate
  参考文献：
  名称：

  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

  摘要：

  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.

  DOI：

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

文献信息

• Asymmetric Synthesis of a (2<i>Z</i>,7<i>E</i>)-Cyclononadiene by an Intramolecular Cycloalkylation and Insight to Its Conformational Properties
  作者：Alexander Deiters、Christian Mück-Lichtenfeld、Roland Fröhlich、Dieter Hoppe

  DOI：10.1021/ol005998h

  日期：2000.8.1

  Here, we report a novel synthesis of a monosubstituted, enantio- and diastereomerically enriched trans-cyclononadienol. The reaction consists of an enantioselective (-)-sparteine-mediated allylic lithiation of an achiral 7-chlorononadienyl carbamate and a subsequent stereospecific intramolecular allyllithium-allyl chloride coupling. The stereochemical course of the cyclization has been determined,

  在这里，我们报告单取代，对映体和非对映异构富集反式环壬二烯醇的新型合成。该反应由非手性7-氯壬二烯基氨基甲酸酯的对映选择性（-）-天冬氨酸介导的烯丙基锂化和随后的立体特异性分子内烯丙基锂-烯丙基氯化物偶联组成。确定了环化的立体化学过程，并通过动力学测量研究了手性九元碳环的高构型稳定性，并通过计算计算使之合理化。
• 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.