(1S,3R,4R)-2-<(1S)-phenylethyl>-2-aza-bicyclo<2.2.1>heptane-3-carboxylic acid ethyl ester | 223473-32-3

• 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: (1S,3R,4R)-2-<(1S)-phenylethyl>-2-aza-bicyclo<2.2.1>heptane-3-carboxylic acid ethyl ester
• 英文别名: (1S,3R,4R)-2-[(S)-1-phenylethyl]-2-azabicyclo[2.2.1]heptane-3-carboxylic acid ethyl ester；ethyl (1S, 3R, 4R)-2-[(S)-1-phenylethyl]-2-azabicyclo[2.2.1]heptane-3-carboxylate；ethyl (1S,3R,4R)-2-[(S)-1-phenylethyl]-2-azabicyclo[2.2.1]heptane-3-carboxylate；ethyl (1S,3R,4R)-2-[(1S)-1-phenylethyl]-2-azabicyclo[2.2.1]heptane-3-carboxylate
• CAS: 223473-32-3
• 化学式: C₁₇H₂₃NO₂
• 分子量: 273.375
• InChiKey: YPNYFYCSKWXEKY-DRPJVOAASA-N

物化性质

• 沸点：
  348.3±25.0 °C(Predicted)
• 密度：
  1.111±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.4
• 重原子数：
  20
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.59
• 拓扑面积：
  29.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (1S,3R,4R)-2-<(1S)-phenylethyl>-2-aza-bicyclo<2.2.1>heptane-3-carboxylic acid ethyl ester 在 lithium aluminium tetrahydride 、 cerium(III) chloride 、 草酰氯 、 氢气 、 palladium(II) hydroxide 、 二甲基亚砜 、 三乙胺 作用下， 以 四氢呋喃 、 乙醇 、 二氯甲烷 为溶剂， 反应 122.0h， 生成 (1S,3R,4R)-2-Azabicyclo[2.2.1]heptane-3-(S)-phenylmethanol
  参考文献：
  名称：

  β-酮基酯与硝基烯烃不对称迈克尔反应的2-基于氮杂降冰片烷的氨基醇有机催化剂

  摘要：

  使用新设计的光学活性的基于2-氮杂降冰片烷的氨基醇有机催化剂，对β-酮酯向硝基烯烃进行了高对映选择性的迈克尔加成反应，从而以良好的化学收率（高达99％）和立体选择性（高达dr = 91：9，最高可达91％ee）。

  DOI：

  10.1002/ejoc.201900308
• 作为产物：
  描述：

  ethyl <(S)-1-phenylethyl>iminoethanoate 在 5%-palladium/activated carbon 、 三氟化硼乙醚 、 氢气 、 potassium carbonate 、 三氟乙酸 作用下， 以 乙醇 为溶剂， 反应 17.0h， 生成 (1S,3R,4R)-2-<(1S)-phenylethyl>-2-aza-bicyclo<2.2.1>heptane-3-carboxylic acid ethyl ester
  参考文献：
  名称：

  β-酮基酯与硝基烯烃不对称迈克尔反应的2-基于氮杂降冰片烷的氨基醇有机催化剂

  摘要：

  使用新设计的光学活性的基于2-氮杂降冰片烷的氨基醇有机催化剂，对β-酮酯向硝基烯烃进行了高对映选择性的迈克尔加成反应，从而以良好的化学收率（高达99％）和立体选择性（高达dr = 91：9，最高可达91％ee）。

  DOI：

  10.1002/ejoc.201900308

文献信息

• Novel chiral bridged azepanes: stereoselective ring expansion of 2-azanorbornan-3-yl methanols
  作者：Elżbieta Wojaczyńska、Ilona Turowska-Tyrk、Jacek Skarżewski

  DOI：10.1016/j.tet.2012.07.028

  日期：2012.9

  conditions with various nucleophiles led to a series of chiral-bridged azepanes with configuration at C-4 dependent on the configuration of the starting alcohol. High yielding, stereoselective ring expansion to novel 2-azabicyclo[3.2.1]octane system occurred via aziridinium intermediates, which were specifically opened by nucleophilic attack at the more substituted carbon.

  2-三氮杂硼烷-3-基甲醇在光延或甲磺酰化条件下与各种亲核试剂的反应导致一系列手性桥连的氮杂环庚烷，其C-4的构型取决于起始醇的构型。通过叠氮基中间体发生了高产立体选择性环扩环至新型2-氮杂双环[3.2.1]辛烷系统，这些中间体是通过亲核性攻击在取代度更高的碳上特异性打开的。
• Azabicyclo compound matrix metalloprotease inibitor and skin preparation
  申请人：Hiruma Takuya

  公开号：US20050009808A1

  公开（公告）日：2005-01-13

  An azabicyclo compound (I) or a salt thereof in accordance with the present invention has an excellent inhibiting action on matrix metalloproteases (MMPs) activity, and is useful for pharmaceutical, cosmetic and skin external compositions. wherein R is H, alkyl, heteroalkyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, acyl, COOR 1 , carbamoyl or SO 2 R 2 (wherein R 1 and R 2 each are alkyl, heteroalkyl, aryl, heteroaryl, arylalkyl or heteroarylalkyl); X is methylene, ethylene or propylene; and is a single bond or a double bond.

  本发明提供的一种氮杂双环化合物(I)或其盐在抑制基质金属蛋白酶(MMPs)活性方面具有优异的作用，并可用于制药、化妆品和皮肤外用组合物中。其中R为H、烷基、杂基烷基、芳基、杂芳基、芳基烷基、杂芳基烷基、酰基、COOR1、氨基甲酰或SO2R2（其中R1和R2各自为烷基、杂基烷基、芳基、杂芳基、芳基烷基或杂芳基烷基）；X为亚甲基、乙烯基或丙烯基；而表示单键或双键。
• Azabicyclo compound matrix metalloprotease inhibitor and skin preparation
  申请人：Shiseido Co., Ltd.

  公开号：US07176217B2

  公开（公告）日：2007-02-13

  An azabicyclo compound (I) or a salt thereof in accordance with the present invention has an excellent inhibiting action on matrix metalloproteases (MMPs) activity, and is useful for pharmaceutical, cosmetic and skin external compositions. wherein R is H, alkyl, heteroalkyl, aryl, heteroaryl, arylalkyl, heteroarylalkyl, acyl, COOR1, carbamoyl or SO2R2 (wherein R1 and R2 each are alkyl, heteroalkyl, aryl, heteroaryl, arylalkyl or heteroarylalkyl); X is methylene, ethylene or propylene; and is a single bond or a double bond.

  本发明所述的一种azabicyclo化合物（I）或其盐对基质金属蛋白酶（MMPs）活性具有优异的抑制作用，可用于制药、化妆品和皮肤外用组合物中。其中R为H、烷基、杂烷基、芳基、杂芳基、芳基烷基、杂芳基烷基、酰基、COOR1、氨基甲酰或SO2R2（其中R1和R2各自为烷基、杂烷基、芳基、杂芳基、芳基烷基或杂芳基烷基）；X为亚甲基、乙烯基或丙烯基；且为单键或双键。
• Synthesis, spectroscopic and computational studies of photochromic azobenzene derivatives with 2-azabicycloalkane scaffold
  作者：Karolina Kamińska、Dominika Iwan、Alex Iglesias-Reguant、Weronika Spałek、Marek Daszkiewicz、Anna Sobolewska、Robert Zaleśny、Elżbieta Wojaczyńska、Stanisław Bartkiewicz

  DOI：10.1016/j.molliq.2022.119869

  日期：2022.10

  In this study we report the synthesis and photochromic properties of chiral azobenzene derivatives based on the 2-azabicycloalkane skeleton. The photochromic properties of newly synthesized family of azobenzene derivatives have been studied using the UV/Vis spectroscopy. The interpretation of spectral features was supported by the results of the electronic-structure calculations. The experimental data

  在这项研究中，我们报告了基于 2-氮杂双环烷烃骨架的手性偶氮苯衍生物的合成和光致变色性质。使用紫外/可见光谱研究了新合成的偶氮苯衍生物家族的光致变色性质。光谱特征的解释得到了电子结构计算结果的支持。实验数据证实 - 典型的偶氮苯 -反式-顺式和顺式-反式的出现分别用可见光和紫外光照射时的光化学反应。另一方面，观察到非典型的热弛豫过程，尤其是在紫外光照射后，这表明热逆反应并不像人们想象的那么简单。位于2-氮杂双环烷烃上的取代基导致所研究化合物的电子结构发生一些变化，反映在电子光谱中谱带形状的变化上。
• A Theoretical and Experimental Study of the Asymmetric Addition of Dialkylzinc toN-(Diphenylphosphinoyl)benzalimine
  作者：Peter Brandt、Christian Hedberg、Klaus Lawonn、Pedro Pinho、Pher G. Andersson

  DOI：10.1002/(sici)1521-3765(19990604)5:6<1692::aid-chem1692>3.0.co;2-m

  日期：1999.6.4

  The mechanism of the enantioselective addition of diethylzinc to N(diphenylphosphinoyl)benzalimine with catalysis by bicyclic 2-azanorbornyl-3-methanols was studied by quantum chemical calculations. The mechanism proved to differ from that of the addition of diethylzinc to aldehydes and also from an earlier proposed mechanism. The results of the calculations were used to identify several factors responsible for the selectivity. The theoretical evaluation was performed in connection with an experimental study of the effects of introducing an additional stereocenter in the ligand. An efficient route to both diastereomers of new bicyclic 2-azanorbornyl-3-methanols with an additional chiral center (the secondary alcohol group) is also presented. In the best case, an enantiomeric excess of up to 97% was obtained with these new ligands.