ethyl (1S,2S,3R,5S)-2-aminopinane-3-carboxylate | 327611-64-3

• 分子结构分类: 有机化合物 - 有机酸及其衍生物 - 羧酸及其衍生物
• 英文名称: ethyl (1S,2S,3R,5S)-2-aminopinane-3-carboxylate
• 英文别名: ethyl (1S,2S,3R,5S)-2-amino-2,6,6-trimethylbicyclo[3.1.1]heptane-3-carboxylate
• CAS: 327611-64-3
• 化学式: C₁₃H₂₃NO₂
• 分子量: 225.331
• InChiKey: TWYASPCEEWJHOF-KEPMVKOISA-N

计算性质

• 辛醇/水分配系数(LogP)：
  2.3
• 重原子数：
  16
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.92
• 拓扑面积：
  52.3
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  ethyl (1S,2S,3R,5S)-2-aminopinane-3-carboxylate 在 lithium aluminium tetrahydride 、 碳酸氢钠 作用下， 以 四氢呋喃 、 水 为溶剂， 反应 3.0h， 生成 (1S,2S,7R,9S)-2,3,10,10-tetramethyl-5-oxa-3-azatricyclo[7.1.1.0^2,7]undecane
  参考文献：
  名称：

  Synthesis and transformations of enantiomeric 1,2-disubstituted monoterpene derivatives

  摘要：

  Regio- and stereospecific addition of chlorosulfonyl isocyanate to (+)- and (-)-alpha -pinene I resulted in enantiomerically pure beta -lactams 2, which were converted to enantiomeric beta -amino esters 3 and 1,3-amino alcohols 4 and 6 with ee >99%. The resulting 1,3-difunctional compounds 3, 4 and 6 were transformed to fused saturated 1,3-heterocycles such as tetrahydro-1,3-oxazines 7 and 9, 2,4-pyrimidinedione 11 and 2-thioxopyrimidin-4-one 13 enantiomers. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(00)00435-3
• 作为产物：
  描述：

  (+)-α-蒎烯 在 盐酸 、 potassium hydroxide 、 sodium sulfite 作用下， 反应 60.0h， 生成 ethyl (1S,2S,3R,5S)-2-aminopinane-3-carboxylate
  参考文献：
  名称：

  α-Pinene-type chiral Schiff bases as tridentate ligands in asymmetric addition reactions

  摘要：

  A group of tridentate Schiff bases derived from (+)-alpha-pinene were synthesized. The steric effects in the transition state, the importance of pi-pi stacking interactions as well as the electronic effects of aryl aldehydes according to Hammett constant values in the enantioselective addition of Et2Zn to aldehydes with the use of Schiff bases as chiral ligands are described. Also, a variety of aldehydes were cyanated using a catalyst prepared in situ from titanium tetraisopropoxide and chiral Schiff bases. The influence of a conjugated double-bond in the cyanation substrates on enantioselectivity was observed. The chemical structures of the chiral Schiff base-titanium alkoxide complexes are discussed based on their H-1 and C-13 NMR spectra. 3D models of the Zn-2-complex catalyst and Ti-complex catalyst containing alpha-pinane-type Schiff bases based on X-ray diffraction experiments are postulated. The models presented were consistent with the reported chirality of the addition product and observed ee. (C) 2011 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2011.03.013

文献信息

• New chiral Schiff bases derived from (+)- and (−)-α-pinenes in the metal complex catalyzed asymmetric oxidation of sulfides
  作者：E. A. Koneva、K. P. Volcho、D. V. Korchagina、N. I. Komarova、A. I. Kochnev、N. F. Salakhutdinov、A. G. Tolstikov

  DOI：10.1007/s11172-008-0017-8

  日期：2008.1

  New chiral Schiff bases were derived from (+)- and (−)-α-pinenes for the first time. Coordinated to vanadium ions, they can be used as ligands in catalytic oxidation of sulfides into chiral sulfoxides. Conditions for the asymmetric oxidation of thioanisole to methyl phenyl sulfoxide in optical purity up to 32% were found. Variation of substituents in the ligand has a significant effect not only on

  新的手性席夫碱首次由 (+)- 和 (-)-α-蒎烯衍生而来。它们与钒离子配位，可用作将硫化物催化氧化为手性亚砜的配体。发现了将苯硫醚不对称氧化为光学纯度高达 32% 的甲基苯基亚砜的条件。配体中取代基的变化不仅对反应的对映选择性有显着影响，而且对形成的亚砜的绝对构型也有显着影响。
• Synthesis, Antimicrobial Evaluation, and Structure–Activity Relationship of α-Pinene Derivatives
  作者：Preeti Dhar、PuiYee Chan、Daniel T. Cohen、Fadi Khawam、Sarah Gibbons、Teresa Snyder-Leiby、Ellen Dickstein、Prashant Kumar Rai、Geeta Watal

  DOI：10.1021/jf403586t

  日期：2014.4.23

  Several (+)- and (-)-alpha-pinene derivatives were synthesized and evaluated for their antimicrobial activity toward Gram-positive bacteria Micrococcus luteus and Staphylococcus aureus, Gram-negative bacterium Escherichia coli, and the unicellular fungus Candida albicans using bioautographic assays. (+)-alpha-Pinene 1a showed modest activity against the test organisms, whereas (-)-alpha-pinene 1b showed no activity at the tested concentration. Of all the alpha-pinene derivatives evaluated, the beta-lactam derivatives (10a and 10b) were the most antimicrobial. The increase in the antimicrobial activity of 10a compared to la ranged from nearly 3.5-fold (C. albicans) to 43-fold (S. aureus). The mean +/- standard deviation for the zone of inhibition (mm) for 10a (C. albicans) was 31.9 +/- 4.3 and that for S. aureus was 51.1 +/- 2.9. Although (-)-alpha-pinene 1b was not active toward the test microorganisms, the corresponding beta-lactam 10b, amino ester 13b, and amino alcohol 14b showed antimicrobial activity toward the test microorganisms. The increase in the antimicrobial activity of lob compared to 1b ranged from 32-fold (S. aureus) to 73-fold (M. luteus). The mean +/- standard deviation for the zone of inhibition (mm) for 10b (S. aureus) was 32.0 +/- 0.60 and that for M. luteus was 73.2 +/- 0.30.
• Derivatives of pinane amino acids as new anticonvulsants
  作者：T. G. Tolstikova、E. A. Morozova、A. V. Pavlova、A. V. Bolkunov、M. P. Dolgikh、E. A. Koneva、K. P. Volcho、N. F. Salakhutdinov、G. A. Tolstikov

  DOI：10.1134/s0012500808100029

  日期：2008.10
• α-Pinene-type chiral Schiff bases as tridentate ligands in asymmetric addition reactions
  作者：Magdalena Jaworska、Ewelina Błocka、Anna Kozakiewicz、Mirosław Wełniak

  DOI：10.1016/j.tetasy.2011.03.013

  日期：2011.3

  A group of tridentate Schiff bases derived from (+)-alpha-pinene were synthesized. The steric effects in the transition state, the importance of pi-pi stacking interactions as well as the electronic effects of aryl aldehydes according to Hammett constant values in the enantioselective addition of Et2Zn to aldehydes with the use of Schiff bases as chiral ligands are described. Also, a variety of aldehydes were cyanated using a catalyst prepared in situ from titanium tetraisopropoxide and chiral Schiff bases. The influence of a conjugated double-bond in the cyanation substrates on enantioselectivity was observed. The chemical structures of the chiral Schiff base-titanium alkoxide complexes are discussed based on their H-1 and C-13 NMR spectra. 3D models of the Zn-2-complex catalyst and Ti-complex catalyst containing alpha-pinane-type Schiff bases based on X-ray diffraction experiments are postulated. The models presented were consistent with the reported chirality of the addition product and observed ee. (C) 2011 Elsevier Ltd. All rights reserved.
• Synthesis and transformations of enantiomeric 1,2-disubstituted monoterpene derivatives
  作者：Zsolt Szakonyi、Tamás Martinek、Anasztázia Hetényi、Ferenc Fülöp

  DOI：10.1016/s0957-4166(00)00435-3

  日期：2000.11

  Regio- and stereospecific addition of chlorosulfonyl isocyanate to (+)- and (-)-alpha -pinene I resulted in enantiomerically pure beta -lactams 2, which were converted to enantiomeric beta -amino esters 3 and 1,3-amino alcohols 4 and 6 with ee >99%. The resulting 1,3-difunctional compounds 3, 4 and 6 were transformed to fused saturated 1,3-heterocycles such as tetrahydro-1,3-oxazines 7 and 9, 2,4-pyrimidinedione 11 and 2-thioxopyrimidin-4-one 13 enantiomers. (C) 2000 Elsevier Science Ltd. All rights reserved.