(2R,3S)-3-Isopropyl-N-(2,4,6-trimethylphenylsulfonyl)-2-(2-trimethylsilylethynyl)aziridine | 253676-40-3

• 分子结构分类: 有机化合物 - 苯类化合物 - 苯和取代衍生物
• 英文名称: (2R,3S)-3-Isopropyl-N-(2,4,6-trimethylphenylsulfonyl)-2-(2-trimethylsilylethynyl)aziridine
• 英文别名: trimethyl-[2-[(2R,3S)-3-propan-2-yl-1-(2,4,6-trimethylphenyl)sulfonylaziridin-2-yl]ethynyl]silane
• CAS: 253676-40-3
• 化学式: C₁₉H₂₉NO₂SSi
• 分子量: 363.596
• InChiKey: KUXZVTBLEXXJLF-ZOVQDZKKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.89
• 重原子数：
  24
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.58
• 拓扑面积：
  45.5
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  (2R,3S)-3-Isopropyl-N-(2,4,6-trimethylphenylsulfonyl)-2-(2-trimethylsilylethynyl)aziridine 、 alkaline earth salt of/the/ methylsulfuric acid 以 四氢呋喃 为溶剂， 反应 1.5h， 以87%的产率得到(5S,aS)-6-methyl-2-trimethylsilyl-5-[N-(2,4,6-trimethylbenzenesulfonyl)amino]-2,3-heptadiene
  参考文献：
  名称：

  Stereoselective Synthesis of Chiral Amino Allenes by Organocopper-Mediated anti-SN2′-Substitution Reaction of Chiral Ethynylaziridines

  摘要：

  Chiral N-protected amino allenes have been synthesized from 3-alkyl-2-ethynylaziridines via organocopper-mediated reactions. Treatment of enantiomerically pure (2R,3S)-2,3-trans-3-alkyl-2-ethynylaziridines with RCu(CN)M (M=Li or MgX) in THF at -78 degrees C affords exclusively the expected (S,S)-amino allenes in high yields in a regio- and stereoselective manner. On the other hand, (2S,3S)-2,3-cis-3-alkyl-2-ethynylaziridines give stereoisomeric (S,R)-amino allenes in comparable high yields. (C) 2000 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0040-4020(00)00136-8
• 作为产物：
  描述：

  2,4,6-三甲基苯磺酰氯 在 四丁基氟化铵 、 三乙胺 、 三苯基膦 、 lithium diisopropyl amide 、 偶氮二甲酸二乙酯 作用下， 以 四氢呋喃 、 正己烷 、 氯仿 、 甲苯 为溶剂， 反应 3.25h， 生成 (2R,3S)-3-Isopropyl-N-(2,4,6-trimethylphenylsulfonyl)-2-(2-trimethylsilylethynyl)aziridine
  参考文献：
  名称：

  方便的手性3-取代的2-乙炔基氮丙啶的合成

  摘要：

  描述了两种从天然α-氨基酸合成手性2-乙炔基氮丙啶的简便方法。氢化钠促进的4-芳基磺酰基氨基-2-溴代烷-2-烯-1-醇甲磺酸酯的叠氮基化反应以高度立体选择性的方式产生反式-2-（1-溴乙烯基）氮丙啶，随后通过叔碳酸钾对氮丙啶进行脱氢溴化反应丁醇钾给出的可分离立体异构体混合物的反式-和顺-2- ethynylaziridines在对映体纯形式的（> 98％ee）的。还介绍了在Mitsunobu条件下由带有乙炔基的手性氨基醇简单合成具有高光学纯度（91-98％ee）的2-乙炔基氮丙啶。

  DOI：

  10.1039/a905027b

文献信息

• A Highly <i>cis</i>-Selective Synthesis of 2-Ethynylaziridines by Intramolecular Amination of Chiral Bromoallenes:  Improvement of Stereoselectivity Based on the Computational Investigation
  作者：Hiroaki Ohno、Kaori Ando、Hisao Hamaguchi、Yusuke Takeoka、Tetsuaki Tanaka

  DOI：10.1021/ja0262277

  日期：2002.12.1

  The base-mediated intramolecular amination of bromoallenes having an axial chirality is described. The treatment of (4S,aR)-4-alkyl-4-[N-(arylsulfonyl)amino]-1-bromobuta-1,2-dienes with NaH in DMF affords 2,3-cis-2-ethynylaziridines in good to excellent selectivity (2,3-cis:trans = 92:8-99:1). The reaction of (4S,aS)-bromoallenes with NaH/DMF also gives 2,3-cis-2-ethynylaziridines selectively (79:21-91:9). These experimental results have been rationalized by 133LYP density functional calculations together with the 6-31 +G(d) basis set and the Onsager solvation model. The transition structures for cis-aziridine formation of both (4S,aR)- and (4S,aS)-bromoallenes in DMF are favored over the corresponding trans transition structures by 4.35 and 1.41 kcal/mol, respectively. Furthermore, the calculations predicted that a less polar solvent gives higher cis selectivity for (4S,aS)-bromoallenes. In fact, improvement of the cis selectivity to 99:1 has been realized by using a less polar solvent such as THF. The cyclization of bromoallenes bearing a beta- or gamma-amino group also affords four- and five-membered azacycles in a highly cis-selective manner.
• Convenient syntheses of chiral 3-substituted 2-ethynylaziridines
  作者：Hiroaki Ohno、Ayako Toda、Yoshiji Takemoto、Nobutaka Fujii、Toshiro Ibuka

  DOI：10.1039/a905027b

  日期：——

  Two convenient methods for the synthesis of chiral 2-ethynylaziridines from natural α-amino acids are described. Sodium hydride-promoted aziridination of mesylates of 4-arylsulfonylamino-2-bromoalk-2-en-1-ols yields trans-2-(1-bromovinyl)aziridines in a highly stereoselective manner, and subsequent dehydrobromination of the aziridines by potassium tert-butoxide gives separable stereoisomeric mixtures

  描述了两种从天然α-氨基酸合成手性2-乙炔基氮丙啶的简便方法。氢化钠促进的4-芳基磺酰基氨基-2-溴代烷-2-烯-1-醇甲磺酸酯的叠氮基化反应以高度立体选择性的方式产生反式-2-（1-溴乙烯基）氮丙啶，随后通过叔碳酸钾对氮丙啶进行脱氢溴化反应丁醇钾给出的可分离立体异构体混合物的反式-和顺-2- ethynylaziridines在对映体纯形式的（> 98％ee）的。还介绍了在Mitsunobu条件下由带有乙炔基的手性氨基醇简单合成具有高光学纯度（91-98％ee）的2-乙炔基氮丙啶。
• Stereoselective Synthesis of Chiral Amino Allenes by Organocopper-Mediated anti-SN2′-Substitution Reaction of Chiral Ethynylaziridines
  作者：Hiroaki Ohno、Ayako Toda、Nobutaka Fujii、Yoshiji Takemoto、Tetsuaki Tanaka、Toshiro Ibuka

  DOI：10.1016/s0040-4020(00)00136-8

  日期：2000.4

  Chiral N-protected amino allenes have been synthesized from 3-alkyl-2-ethynylaziridines via organocopper-mediated reactions. Treatment of enantiomerically pure (2R,3S)-2,3-trans-3-alkyl-2-ethynylaziridines with RCu(CN)M (M=Li or MgX) in THF at -78 degrees C affords exclusively the expected (S,S)-amino allenes in high yields in a regio- and stereoselective manner. On the other hand, (2S,3S)-2,3-cis-3-alkyl-2-ethynylaziridines give stereoisomeric (S,R)-amino allenes in comparable high yields. (C) 2000 Elsevier Science Ltd. All rights reserved.