(1R,2R,5S,7R)-2,8,8-trimethyl-3-azatricyclo[5.1.1.0^2,5]nonan-4-one | 328010-06-6

• 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: (1R,2R,5S,7R)-2,8,8-trimethyl-3-azatricyclo[5.1.1.0^2,5]nonan-4-one
• 英文别名: (1R,2R,5S,7R)-2,8,8-trimethyl-3-azatricyclo[5.1.1.0(2,5)]nonan-4-one；(1R,2R,5S,7R)-2,8,8,Trimethyl-3-azatricyclo[5.1.1.0(2,5)]nonane-4-one；(1R,2R,5S,7R)-2,8,8-trimethyl-3-azatricyclo[5.1.1.02,5]nonan-4-one
• CAS: 328010-06-6
• 化学式: C₁₁H₁₇NO
• 分子量: 179.262
• InChiKey: KUAXJPRPFKYSME-RFOGZPIASA-N

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

安全信息

• 海关编码：
  2933990090

反应信息

• 作为反应物：
  描述：

  (1R,2R,5S,7R)-2,8,8-trimethyl-3-azatricyclo[5.1.1.0^2,5]nonan-4-one 在 盐酸 、 碳酸氢钠 作用下， 反应 12.0h， 生成 ethyl (1R,2R,3S,5R)-2-(ethoxycarbonylamino)pinane-3-carboxylate
  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：

  (1R,2R,5S,7R)-2,8,8-trimethyl-4-oxo-3-azatricyclo[5.1.1.02,5]nonane-3-sulfonyl chloride 在 氢氧化钾 、 sodium sulfite 作用下， 以 乙醚 、 水 为溶剂， 以5.4 g的产率得到(1R,2R,5S,7R)-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

• Remote, Late-Stage Oxidation of Aliphatic C–H Bonds in Amide-Containing Molecules
  作者：Takeshi Nanjo、Emilio C. de Lucca、M. Christina White

  DOI：10.1021/jacs.7b07665

  日期：2017.10.18

  systematic study of the main features that makes remote oxidations of amides in peptide settings possible, we developed an imidate salt protecting strategy that employs methyl trifluoromethanesulfonate as a reversible alkylating agent. The imidate salt strategy enables, for the first time, remote, nondirected, site-selective C(sp3)-H oxidation with Fe(PDP) and Fe(CF3PDP) catalysis in the presence of a broad

  含酰胺分子在天然产物、药物和材料科学中无处不在。由于它们的中间电子丰富性，它们不适合任何先前开发的已知可实现远程脂肪族 CH 氧化的 N 保护策略。使用从使肽设置中酰胺的远程氧化成为可能的主要特征的系统研究中收集的信息，我们开发了一种亚氨酸盐保护策略，该策略采用三氟甲磺酸甲酯作为可逆烷化剂。亚胺酸盐策略首次在广泛的叔酰胺、苯胺、2 中使用 Fe(PDP) 和 Fe(CF3PDP) 催化进行远程、非定向、位点选择性 C(sp3)-H 氧化。 -吡啶酮和氨基甲酸酯功能。二级和一级酰胺可以被掩盖为 N-Ns 酰胺以进行远程氧化。这种新颖的亚胺酸酯策略促进了更广泛的医学上重要分子的后期氧化，并可能用于其他不耐受酰胺官能团的 CH 氧化和金属介导的反应。
• 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。
• 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.
• 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.