l-8-phenylmenthyl (1R,3S)-2,2-dicyano-3-(4-pyridyl)cyclopropanecarboxylate | 326487-60-9

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: l-8-phenylmenthyl (1R,3S)-2,2-dicyano-3-(4-pyridyl)cyclopropanecarboxylate
• 英文别名: [(1R,2S,5R)-5-methyl-2-(2-phenylpropan-2-yl)cyclohexyl] (1R,3S)-2,2-dicyano-3-pyridin-4-ylcyclopropane-1-carboxylate
• CAS: 326487-60-9
• 化学式: C₂₇H₂₉N₃O₂
• 分子量: 427.546
• InChiKey: AUELDMDHBRJYTO-JXIQEMPDSA-N

物化性质

• 沸点：
  602.2±55.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  5
• 重原子数：
  32
• 可旋转键数：
  6
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  86.8
• 氢给体数：
  0
• 氢受体数：
  5

反应信息

• 作为反应物：
  描述：

  sodium methylate 、 l-8-phenylmenthyl (1R,3S)-2,2-dicyano-3-(4-pyridyl)cyclopropanecarboxylate 以 二氯甲烷 为溶剂， 反应 0.08h， 以31%的产率得到(1S,5R,6S)-2,2-dimethoxy-4-oxo-6-pyridin-4-yl-3-oxabicyclo[3.1.0]hexane-1-carbonitrile
  参考文献：
  名称：

  Enantioselective cyclopropanation reaction using a conformationally fixed pyridinium ylide through a cation–π interaction

  摘要：

  Using a chiral pyridinium ylide with a fixed conformation through a cation-pi interaction performs enantioselective cyclo-propanation of electron-deficient olefins. H-1 NMR, X-ray structural analysis and DFT calculations elucidated the self-complexation and the face-to-face arrangement between the pyridinium and the phenyl rings. The absolute configuration of the product was determined after conversion into a bicyclic cyclopropane derivative. (c) 2006 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetlet.2006.11.142
• 作为产物：
  描述：

  (1R,2S,5R)-(+)-5-methyl-2-(1-methyl-1-phenylethyl)cyclohexyl chloroacetate 在 三乙胺 作用下， 以 二氯甲烷 为溶剂， 生成 l-8-phenylmenthyl (1R,3S)-2,2-dicyano-3-(4-pyridyl)cyclopropanecarboxylate
  参考文献：
  名称：

  8-苯基薄荷酯基团吡啶鎓叶立德非对映选择性环丙烷反应中取代基对吡啶环的影响

  摘要：

  研究了 β-取代的亚甲基丙二腈与 (-)-8-苯基薄荷基 α-吡啶鎓乙酸酯的内鎓盐之间的反应，得到带有两个氰基和一个羧酸酯基的活化环丙烷。在叔丁基取代底物的优化溶剂条件下，反式异构体的非对映选择性高达 91:9。使用 4-甲氧基吡啶代替吡啶时选择性增加到 96:4，而 N,N-二乙基烟酰胺的选择性通常较低。通过 X 射线结构分析确定主要的 4-吡啶基取代的环丙烷为反式 1R。

  DOI：

  10.3987/com-05-s(t)56

文献信息

• Stereoselective formation of activated cyclopropanes with pyridinium ylides bearing a (−)-8-phenylmenthyl group as the chiral auxiliary
  作者：Satoshi Kojima、Kouji Fujitomo、Yoshihiro Shinohara、Makoto Shimizu、Katsuo Ohkata

  DOI：10.1016/s0040-4039(00)01743-3

  日期：2000.12

  The reaction of various mono-substituted methylidenemalononitriles with (-)-8-phenylmenthyl alpha -pyridiniumacetate in the presence of base afforded the corresponding dicyanocyclopropane compounds with exclusive trans-selectivity and good diastereoselectivity (up to 86.14). The stereochemistry of the major products were determined to be of 1R configuration by X-ray structural analysis of the crystalline tuans -2,2-dicyano-3-(4-pyridyl)cyclopropanecarboxylate. The geometric and diastereofacial selectivities were rationalized assuming anti-periplanar approach in the open-chain model, followed by epimerization and then cyclization to give the cyclopropane compounds. (C) 2000 Elsevier Science Ltd. All rights reserved.
• The Effect of Substituents on the Pyridine Ring in the Diastereoselective Cyclopropa- nation Reaction of Pyridinium Ylides Bear- ing an 8-Phenylmenthyl Ester Group
  作者：Satoshi Kojima、Kouji Fujitomo、Yoshiaki Itoh、Kyoko Hiroike、Masaaki Murakami、Katsuo Ohkata

  DOI：10.3987/com-05-s(t)56

  日期：——

  The reaction between β-substituted methylidenemalononitriles and the ylide from (-)-8-phenylmenthyl α-pyridiniumacetate, which affords activated cyclopropanes bearing two cyano groups and one carboxylic ester group, was examined. The trans isomer was obtained in up to 91:9 diastereoselectivity under optimized solvent conditions for the t-butyl substituted substrate. The selectivity increased to 96:4

  研究了 β-取代的亚甲基丙二腈与 (-)-8-苯基薄荷基 α-吡啶鎓乙酸酯的内鎓盐之间的反应，得到带有两个氰基和一个羧酸酯基的活化环丙烷。在叔丁基取代底物的优化溶剂条件下，反式异构体的非对映选择性高达 91:9。使用 4-甲氧基吡啶代替吡啶时选择性增加到 96:4，而 N,N-二乙基烟酰胺的选择性通常较低。通过 X 射线结构分析确定主要的 4-吡啶基取代的环丙烷为反式 1R。
• Enantioselective cyclopropanation reaction using a conformationally fixed pyridinium ylide through a cation–π interaction
  作者：Shinji Yamada、Jun Yamamoto、Emiko Ohta

  DOI：10.1016/j.tetlet.2006.11.142

  日期：2007.1

  Using a chiral pyridinium ylide with a fixed conformation through a cation-pi interaction performs enantioselective cyclo-propanation of electron-deficient olefins. H-1 NMR, X-ray structural analysis and DFT calculations elucidated the self-complexation and the face-to-face arrangement between the pyridinium and the phenyl rings. The absolute configuration of the product was determined after conversion into a bicyclic cyclopropane derivative. (c) 2006 Elsevier Ltd. All rights reserved.