(2S,3S)-2-Ethynyl-3-isopropyl-N-(2,4,6-trimethylphenylsulfonyl)aziridine | 220765-48-0

• 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: (2S,3S)-2-Ethynyl-3-isopropyl-N-(2,4,6-trimethylphenylsulfonyl)aziridine
• 英文别名: (2S,3S)-2-ethynyl-3-propan-2-yl-1-(2,4,6-trimethylphenyl)sulfonylaziridine
• CAS: 220765-48-0
• 化学式: C₁₆H₂₁NO₂S
• 分子量: 291.414
• InChiKey: ZCJXOYUFYCGVIA-GIIGEWEBSA-N

物化性质

• 沸点：
  400.7±55.0 °C(Predicted)
• 密度：
  1.18±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  3.5
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 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：

  (2S,3S)-2-Ethynyl-3-isopropyl-N-(2,4,6-trimethylphenylsulfonyl)aziridine 在 sodium hydride 作用下， 以 N,N-二甲基甲酰胺 为溶剂， 反应 10.0h， 以95%的产率得到(2R,3S)-2-Ethynyl-3-isopropyl-N-(2,4,6-trimethylphenylsulfonyl)aziridine
  参考文献：
  名称：

  通过碱介导的溴代烯类分子内胺化的立体选择性合成手性2,3-顺-2-乙炔基氮丙啶。

  摘要：

  [反应：见正文]提出了一种新的立体选择性合成方法，由氨基丙二烯合成2,3-顺-2-乙炔基氮丙啶。氢化钠介导的（4S，aS）-4-烷基-4- [N-（芳基磺酰基）氨基] -1-溴丁烯-1,2-二烯的分子内胺化反应生成2,3-顺式和2， 3-反式-2-乙炔基氮丙啶类化合物，其中顺式异构体占主导地位（79：21-89：11），（4S，aR）异构体的胺化反应可提供具有优异选择性的2,3-顺式氮丙啶类化合物（91：9- 100：0）。还描述了通过一系列反应（甲磺酸介导的开环反应，溴化和叠氮化）将2，3-反式-2-乙炔基氮丙啶转化成相应的顺式异构体。

  DOI：

  10.1021/ol016027k
• 作为产物：
  描述：

  (4S,2Z)-2-Bromo-5-methyl-4-[N-(2,4,6-trimethylphenylsulfonyl)amino]hex-2-en-1-ol 在 吡啶 、 potassium tert-butylate 、 sodium hydride 、 二甲基亚砜 作用下， 反应 6.0h， 生成 (2S,3S)-2-Ethynyl-3-isopropyl-N-(2,4,6-trimethylphenylsulfonyl)aziridine
  参考文献：
  名称：

  A convenient synthesis of activated enantiomerically pure 2-ethynylaziridines

  摘要：

  2,3-cis- and 2,3-trans-N-Arylsulfonyl-2-ethynylaziridines with high enantiomeric purity have been synthesized. N-Protected amino aldehydes synthesized from natural alpha-amino acids were successively treated with Ph3P=C(Br)CO2Me, DIBAL, MsCl-Et3N, NaH in DMSO, and tert-BuOK in THF to yield 2-ethynylaziridines in good to high yields. (C) 1998 Elsevier Science Ltd. All rights reserved.

  DOI：

  10.1016/s0957-4166(98)00406-6

文献信息

• 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。
• 2-Ethynylaziridines as Chiral Carbon Nucleophiles:  Stereoselective Synthesis of 1,3-Amino Alcohols with Three Stereocenters via Allenylindium Reagents Bearing a Protected Amino Group
  作者：Hiroaki Ohno、Hisao Hamaguchi、Tetsuaki Tanaka

  DOI：10.1021/jo005756v

  日期：2001.3.1

  H(2)O. Stereoselective addition of the allenylindium to aliphatic or aromatic aldehydes affords 1,3-amino alcohols bearing three contiguous chiral centers: while 2,3-trans-2-ethynylaziridines yield syn,syn-2-ethynyl-1,3-amino alcohols predominantly, 2,3-cis-aziridines give anti,syn isomers selectively. Synthesis of highly substituted ethynylazetidines is also described.

  通过在Pd（PPh（3））（4）和H（2）O存在下用InI处理N-保护的3-烷基-2-乙炔基氮丙啶，可以有效地制备带有保护氨基的烯丙基铟试剂。将烯丙基铟立体选择性地加成到脂肪族或芳香族醛上，可得到带有三个连续手性中心的1,3-氨基醇：而2,3-反式-2-乙炔基氮丙啶主要产生syn，syn-2-ethynyl-1,3-氨基醇， 2,3-顺-氮丙啶类化合物选择性地产生抗，syn异构体。还描述了高度取代的乙炔基氮杂环丁烷的合成。
• 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.
• Umpolung of Chiral 2-Ethynylaziridines:  Indium(I)-Mediated Stereoselective Synthesis of Nonracemic 1,3-Amino Alcohols Bearing Three Chiral Centers, Catalyzed by Palladium(0)
  作者：Hiroaki Ohno、Hisao Hamaguchi、Tetsuaki Tanaka

  DOI：10.1021/ol006089v

  日期：2000.7.1

  [GRAPHICS]Treatment of 3-alkyl-2-ethynylaziridines with Inl in the presence of Pd(PPh3)(4) and H2O gave allenylindium reagents bearing a protected amino group in high yields. Stereoselective addition of the allenylindium to aldehydes affords 2-ethynyl-1,3-amino alcohols bearing three chiral centers in good yields.
• 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.