(1S,2S,5R,7S)-2,8,8-trimethyl-3-azatricyclo[5.1.1.0^2,5]nonan-4-one | 35182-62-8

• 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: (1S,2S,5R,7S)-2,8,8-trimethyl-3-azatricyclo[5.1.1.0^2,5]nonan-4-one
• 英文别名: (1S,2S,5R,7S)-2,8,8-trimethyl-3-azatricyclo[5.1.1.0(2,5)]nonan-4-one；2,8,8-Trimethyl-3-azatricyclo<5.1.1.0^2.5>nonan-4-on；2,8,8-Trimethyl-3-azatricyclo[5.1.1.0^2.5]nonan-4-on；(1S,2S,5R,7S)-2,8,8-Trimethyl-3-azatricyclo[5.1.1.0~2,5~]nonan-4-one；(1S,2S,5R,7S)-2,8,8-trimethyl-3-azatricyclo[5.1.1.02,5]nonan-4-one
• CAS: 35182-62-8
• 化学式: C₁₁H₁₇NO
• 分子量: 179.262
• InChiKey: KUAXJPRPFKYSME-OFHVYEONSA-N

物化性质

• 沸点：
  303.6±11.0 °C(Predicted)
• 密度：
  1.070±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  13
• 可旋转键数：
  0
• 环数：
  4.0
• sp3杂化的碳原子比例：
  0.91
• 拓扑面积：
  29.1
• 氢给体数：
  1
• 氢受体数：
  1

反应信息

• 作为反应物：
  描述：

  (1S,2S,5R,7S)-2,8,8-trimethyl-3-azatricyclo[5.1.1.0^2,5]nonan-4-one 在 4-二甲氨基吡啶 、 水 、 三乙胺 、 lithium hydroxide 、 氯甲酸异丁酯 作用下， 以 四氢呋喃 、 二氯甲烷 、 乙腈 为溶剂， 反应 45.0h， 生成 tert-butyl (1S,2S,3R,5S)-2,6,6-trimethyl-3-{[(R)-1-phenylethyl]carbamoyl}bicyclo[3.1.1]heptan-2-ylcarbamate
  参考文献：
  名称：

  立体选择性合成含β-氨基酸的（+）-α-P烯的手性吡咯烷衍生物

  摘要：

  摘要 我们报道了几种含有β-氨基酸部分的对映体纯吡咯烷衍生物的合成。这些新型手性化合物是通过将立体定向的氯磺酰基异氰酸酯（CSI）添加到易于获得的天然萜烯（+）-α-pine烯中制备的。使用混合酸酐活化方法将N -Boc保护的β-氨基酸衍生物与各种笨重的胺和氨基酸偶联，然后进行N-脱保护，以良好的产率得到相应的手性氨基酰胺。尽管预期在基于α-pine烯的杂环中存在严重的空间位阻，但氨基酰胺和氨基酯与N -Cbz保护的酰氯的有效偶联（S脯氨酸以高收率提供了相应的吡咯烷二烯pin衍生物。此外，方便的合成Ñ -Cbz-和Ñ -Boc-单保护（小号）-prolinamine报道。 我们报道了几种含有β-氨基酸部分的对映体纯吡咯烷衍生物的合成。这些新型手性化合物是通过将立体定向的氯磺酰基异氰酸酯（CSI）添加到易于获得的天然萜烯（+）-α-pine烯中制备的。使用混合酸酐活化方法将N -Boc保护的

  DOI：

  10.1055/s-0033-1339291
• 作为产物：
  描述：

  在 氢氧化钾 、 sodium sulfite 作用下， 以 乙醚 、 水 为溶剂， 以5.7 g的产率得到(1S,2S,5R,7S)-2,8,8-trimethyl-3-azatricyclo[5.1.1.0^2,5]nonan-4-one
  参考文献：
  名称：

  源自金属配合物中 (+)- 和 (-)-α-蒎烯的新型手性席夫碱催化硫化物的不对称氧化

  摘要：

  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。

  DOI：

  10.1007/s11172-008-0017-8

文献信息

• Unusual Temperature-Induced Retention Behavior of Constrained β-Amino Acid Enantiomers on the Zwitterionic Chiral Stationary Phases ZWIX(+) and ZWIX(-)
  作者：István Ilisz、Zoltán Pataj、Zsanett Gecse、Zsolt Szakonyi、Ferenc Fülöp、Wolfgang Lindner、Antal Péter

  DOI：10.1002/chir.22333

  日期：2014.8

  The effects of temperature on the chiral recognition of cyclic β‐amino acid enantiomers on zwitterionic [Chiralpak ZWIX(+) and ZWIX(–)] chiral stationary phases were investigated. Experiments were performed at different mobile phase compositions and under 10°C column temperature increments in the temperature range 10–50°C. Apparent thermodynamic parameters and Tiso values were calculated from plots

  研究了温度对两性离子型[Chiralpak ZWIX（+）和ZWIX（-）]手性固定相上环状β-氨基酸对映体的手性识别的影响。实验是在不同的流动相组成下，在10°C的柱温下，在10–50°C的温度范围内进行的。根据ln k和lnα与1 / T的关系图计算了表观热力学参数和T iso值，分别。观察到异常的温度行为，尤其是在ZWIX（–）色谱柱上，在该色谱柱上使用包含25 mM三乙胺和50 mM甲酸作为流动相的MeOH / MeCN（50/50 v / v）导致了非线性Van't Hoff图并随着温度的升高而延长保留时间。在两根色谱柱上，均观察到了焓和熵驱动的分离。手性26：385–393，2014。©2014 Wiley Periodicals，Inc.
• 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.
• Regio- and stereoselective synthesis of the enantiomers of monoterpene-based β-amino acid derivatives
  作者：Zsolt Szakonyi、Tamás A. Martinek、Reijo Sillanpää、Ferenc Fülöp

  DOI：10.1016/j.tetasy.2007.09.028

  日期：2007.10

  The regio- and stereospecific addition of chlorosulfonyl isocyanate to cis-delta-pinene enantiomers has furnished monoterpene-fused beta-lactams. The observed regioselectivity can be explained by ab initio DFT modeling of transition state structures. In contrast with the less reactive alpha-pinane-fused beta-lactam 4, the resulting beta-lactams 5 and 13 containing an amino group connected to a secondary carbon possess similar reactivity to the cycloalkane-fused analogues and can be easily converted to the beta-amino acid and its protected derivatives. The base-catalyzed isomerization of the cis-amino ester afforded the corresponding trans-amino ester in moderate yield. (c) 2007 Published by Elsevier Ltd.
• 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.
• 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.