1-{(4S)-4-benzyl-4,5-dihydro-1,3-oxazol-2-yl}-(1S)-2-methylpropylamine | 868135-33-5

• 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: 1-{(4S)-4-benzyl-4,5-dihydro-1,3-oxazol-2-yl}-(1S)-2-methylpropylamine
• 英文别名: 1-((4S)-4-benzyl-4,5-dihydro-oxazol-2-yl)-(2S)-2-methylpropylamine；(1S)-1-[(4S)-4-benzyl-4,5-dihydro-1,3-oxazol-2-yl]-2-methylpropan-1-amine
• CAS: 868135-33-5
• 化学式: C₁₄H₂₀N₂O
• 分子量: 232.326
• InChiKey: XRHUFBJRNYQYEA-STQMWFEESA-N

物化性质

• 沸点：
  334.6±25.0 °C(Predicted)
• 密度：
  1.12±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.2
• 重原子数：
  17
• 可旋转键数：
  4
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  47.6
• 氢给体数：
  1
• 氢受体数：
  3

反应信息

• 作为反应物：
  描述：

  1-{(4S)-4-benzyl-4,5-dihydro-1,3-oxazol-2-yl}-(1S)-2-methylpropylamine 、 3,4-二甲氧基-3-环丁烯-1,2-二酮 以 甲醇 为溶剂， 反应 4.0h， 以75%的产率得到3,4-bis((S)-1-((S)-4-benzyl-4,5-dihydrooxazol-2-yl)-2-methylpropylamino)cyclobut-3-ene-1,2-dione
  参考文献：
  名称：

  Enantioselective Friedel–Crafts alkylation of indoles with β,γ-unsaturated α-ketoesters catalyzed by new squaramide-linked bisoxazoline–Zn(OTf)2 complexes

  摘要：

  Enantioselective Friedel-Crafts alkylation reactions of indoles with beta,gamma-unsaturated alpha-ketoesters catalyzed by novel chiral C-2-symmetric squaramide-linked bisoxazoline-Zn(OTf)(2) complexes were investigated. The corresponding indole ketoesters were obtained in good to excellent yields (up to 98%) and with high enantioselectivities (up to 94% ee). This is the first report on the use of chiral squaramide-linked bisoxazoline SQBOX in a catalytic enanitioselective Friedel-Crafts alkylation reaction. (C) 2014 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tetasy.2014.05.011
• 作为产物：
  描述：

  1-{(4S)-4-benzyl-4,5-dihydro-1,3-oxazol-2-yl}-(1S)-2-methylpropylcarbamic acid 9H-fluoren-9-ylmethyl ester 在 哌啶 作用下， 以 甲醇 为溶剂， 生成 1-{(4S)-4-benzyl-4,5-dihydro-1,3-oxazol-2-yl}-(1S)-2-methylpropylamine
  参考文献：
  名称：

  通过 Pd(II)/Pd(0) 催化对烷基胺进行对映选择性 γ-C(sp3)-H 活化

  摘要：

  使用手性乙酰基保护的氨基甲基恶唑啉配体 (APAO) 首次实现了 Pd(II) 催化的烷基胺通过去对称化和动力学拆分的对映选择性 γ-C(sp3)-H 交叉偶联。多种芳基和乙烯基硼试剂可用作偶联伙伴。手性γ-芳基化烷基胺产物进一步转化为手性2-取代的1,2,3,4-四氢喹啉和螺-吡咯烷，作为天然产物和生物活性分子中的重要结构基序。

  DOI：

  10.1021/jacs.8b01094

文献信息

• Stereochemical Diversity in Chiral Ligand Design:  Discovery and Optimization of Catalysts for the Enantioselective Addition of Allylic Halides to Aldehydes
  作者：Jae-Young Lee、Jeremie J. Miller、Steven S. Hamilton、Matthew S. Sigman

  DOI：10.1021/ol050528e

  日期：2005.4.1

  simple amino acids that promote the Cr-catalyzed enantioselective addition of allylic halides to aldehydes in up to 95% ee. The Cr-catalyzed allylation using ligand 1d is rather insensitive to the nature of the allylic bromide (crotyl, allyl, and methallyl) in that >90% ee is observed for all three bromides evaluated in the addition to benzaldehyde.

  [反应：见正文]我们鉴定了一组新的立体化学不同的恶唑啉配体，这些配体衍生自简单的氨基酸，这些氨基酸可促进Cr催化将烯丙基卤化物以高达95％ee的形式对醛进行对映选择性加成。使用配体1d的Cr催化的烯丙基化对烯丙基溴（巴豆基，烯丙基和甲基烯丙基）的性质相当不敏感，因为在除苯甲醛外评估的所有三种溴化物均观察到> 90％ee。
• Modular syntheses of oxazolinylamine ligands and characterization of group 10 metal complexes
  作者：Christine A Caputo、Florentino d S Carneiro、Michael C Jennings、Nathan D Jones

  DOI：10.1139/v06-188

  日期：2007.2.1

  The syntheses of aminoalkyloxazoline and pyrrolidinyloxazoline ligands, each of which bear a pair of chiral centres, by both known and new routes are reported. Variable temperature NMR studies show that the known stepwise syntheses of the pyrrolidinyl compounds are not complicated by epimerization; however, coordination of one of the aminoalkyl derivatives to Pt(II) under conditions of prolonged heating to 80 °C does give mixtures of diastereomeric N,N ′-chelated complexes that result from inversion of the chiral centre associated with the aminoalkyl fragment. A new synthesis of pyrrolidinyloxazoline ligands that involves the Zn-catalyzed cyclization of Cbz-protected 2-cyanopyrrolidine and β-amino alcohols is also reported. This procedure offers the advantages of economy, shorter time, and fewer purification steps over the previously reported synthesis. In addition, the crystal structure of an enantiopure Pd(II) complex of an N,N ′-chelated pyrrolidinyloxazoline is disclosed. This compound has a pseudo-C₂ axis of symmetry, which may make it suitable for asymmetric catalytic applications.Key words: chiral ligands, ligand design, oxazolines, variable temperature NMR spectroscopy, asymmetric catalysis, coordination compounds, palladium, platinum

  报告采用已知路线和新路线合成了氨基烷基恶唑啉和吡咯烷基恶唑啉配体，每种配体都带有一对手性中心。变温核磁共振研究表明，已知的吡咯烷基化合物的逐步合成过程不会因表聚而复杂化；然而，在长时间加热至 80 °C 的条件下，将其中一种氨基烷基衍生物与 Pt(II) 配位，确实会产生非对映的 N,N′-螯合复合物混合物，这是因为与氨基烷基片段相关的手性中心发生了反转。此外，还报道了一种吡咯烷基噁唑啉配体的新合成方法，该方法涉及 Zn 催化的 Cbz 保护的 2-氰基吡咯烷和 β-氨基醇的环化。与之前报道的合成方法相比，该方法具有经济、时间短、纯化步骤少等优点。此外，还公开了一种 N,N′-螯合吡咯烷基噁唑啉的对映体纯 Pd(II) 复合物的晶体结构。关键词：手性配体；配体设计；噁唑啉；变温核磁共振光谱；不对称催化；配位化合物；钯；铂
• Cu^I -Catalysed Enantioselective Alkyl 1,4-Additions to (<i>E</i> )-Nitroalkenes and Cyclic Enones with Phosphino-Oxazoline Ligands
  作者：Minkyeong Shin、Minji Gu、Sung Soo Lim、Min-Jae Kim、JuHyung Lee、HyeongGyu Jin、Yun Hee Jang、Byunghyuck Jung

  DOI：10.1002/ejoc.201800476

  日期：2018.6.29

  New phosphino‐oxazoline ligands have been developed, and the ligands have been used for Cu‐catalysed enantioselective conjugate additions to (E)‐nitroalkenes.

  已开发出新的膦基-恶唑啉配体，该配体已被用于铜催化的（E）-硝基烯烃的铜对映体选择性共轭加成反应。
• Enantioselective γ-C(sp³)–H Activation of Alkyl Amines via Pd(II)/Pd(0) Catalysis
  作者：Qian Shao、Qing-Feng Wu、Jian He、Jin-Quan Yu

  DOI：10.1021/jacs.8b01094

  日期：2018.4.25

  Pd(II)-catalyzed enantioselective γ-C(sp3)-H cross-coupling of alkyl amines via desymmetrization and kinetic resolution has been realized for the first time using chiral acetyl-protected aminomethyl oxazoline ligands (APAO). A diverse range of aryl- and vinyl-boron reagents can be used as coupling partners. The chiral γ-arylated alkylamine products are further transformed into chiral 2-substituted 1,2,3,4-

  使用手性乙酰基保护的氨基甲基恶唑啉配体 (APAO) 首次实现了 Pd(II) 催化的烷基胺通过去对称化和动力学拆分的对映选择性 γ-C(sp3)-H 交叉偶联。多种芳基和乙烯基硼试剂可用作偶联伙伴。手性γ-芳基化烷基胺产物进一步转化为手性2-取代的1,2,3,4-四氢喹啉和螺-吡咯烷，作为天然产物和生物活性分子中的重要结构基序。
• Enantioselective Friedel–Crafts alkylation of indoles with β,γ-unsaturated α-ketoesters catalyzed by new squaramide-linked bisoxazoline–Zn(OTf)2 complexes
  作者：Sheng-Jian Jia、Da-Ming Du

  DOI：10.1016/j.tetasy.2014.05.011

  日期：2014.7

  Enantioselective Friedel-Crafts alkylation reactions of indoles with beta,gamma-unsaturated alpha-ketoesters catalyzed by novel chiral C-2-symmetric squaramide-linked bisoxazoline-Zn(OTf)(2) complexes were investigated. The corresponding indole ketoesters were obtained in good to excellent yields (up to 98%) and with high enantioselectivities (up to 94% ee). This is the first report on the use of chiral squaramide-linked bisoxazoline SQBOX in a catalytic enanitioselective Friedel-Crafts alkylation reaction. (C) 2014 Elsevier Ltd. All rights reserved.