2-(tert-butoxycarbonylamino)benzyl-2-cyanocyclopentanone | 1219681-42-1

• 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: 2-(tert-butoxycarbonylamino)benzyl-2-cyanocyclopentanone
• 英文别名: tert-butyl ((1-cyano-2-oxocyclopentyl)(phenyl)methyl)carbamate
• CAS: 1219681-42-1
• 化学式: C₁₈H₂₂N₂O₃
• 分子量: 314.384
• InChiKey: HTBPRBXDDBTGPK-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.52
• 重原子数：
  23.0
• 可旋转键数：
  3.0
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  79.19
• 氢给体数：
  1.0
• 氢受体数：
  4.0

反应信息

• 作为产物：
  描述：

  benzaldehyde N-boc imine 、 2-氰基环戊酮 在 scandium isopropoxide 、 (RS)-N-(2-hydroxyphenyl)-2-(2-hydroxybenzoylamino)-3-methylbutylamide 作用下， 以 正己烷 、 二氯甲烷 、 异丙醇 为溶剂， 反应 20.0h， 生成 (R)-2-((S)-tert-butoxycarbonylamino)benzyl-2-cyanocyclopentanone 、 2-(tert-butoxycarbonylamino)benzyl-2-cyanocyclopentanone
  参考文献：
  名称：

  Solvent-Dependent Self-Discrimination of Bis(2-hydroxyphenyl)diamides

  摘要：

  AbstractSolvent‐dependent, self‐discrimination of diamides is described. Mixing a solution of (R)‐1 a and (S)‐1 a, which are valine‐derived, bis(2‐hydroxyphenyl)diamide‐bearing, multiple hydrogen‐bonding modules, in dichloromethane immediately led to the formation of a thick suspension comprising a 1:1 heterochiral aggregate of 1 a. The solubility of heterochiral 1 a was substantially lower in halogenated solvents than in ethyl acetate. A perusal of racemic crystal structures obtained from chloroform and ethyl acetate revealed a significant difference in the crystal‐packing pattern, which is likely to be the basis for the pronounced difference in solubility. Specific self‐discrimination of 1 a in an ensemble of eight structurally related molecules showcased the specific aggregation through the hydrogen‐bonding network of the bis(2‐hydroxyphenyl)diamide framework. The low solubility of heterochiral 1 a in halogenated solvent was exploited to achieve high stereoselectivity in a catalytic asymmetric reaction by using a low enantiomeric excess sample of 1 a.

  DOI：

  10.1002/chem.201000321

文献信息

• Enantio- and Diastereoselective Mannich-Type Reactions of α-Cyano Ketones with<i>N</i>-Boc Aldimines Catalyzed by Chiral Bifunctional Urea
  作者：Ju Hee Lee、Dae Young Kim

  DOI：10.1002/adsc.200900268

  日期：2009.8

  The catalytic enantioselective electrophilic Mannich-type reaction promoted by chiral bifunctional organocatalysts is described. The treatment of α-cyano ketones with N-Boc-aldimines under mild reaction conditions afforded the corresponding β-amino-α-cyano ketones with excellent diastereoselectivities (up to syn/anti=100/0), and excellent enantioselectivities (up to 99% ee).

  描述了由手性双官能有机催化剂促进的催化对映选择性亲电曼尼希型反应。在温和的反应条件下，用N -Boc-醛亚胺处理α-氰基酮，得到相应的β-氨基-α-氰基酮，具有非对映选择性（高达syn / anti = 100/0）和出色的对映选择性（高达99） ％ee）。
• A Carbon Nanotube Confinement Strategy to Implement Homogeneous Asymmetric Catalysis in the Solid Phase
  作者：Kazuki Hashimoto、Naoya Kumagai、Masakatsu Shibasaki

  DOI：10.1002/chem.201406402

  日期：2015.3.9

  recyclable asymmetric catalyst has been developed based on the self‐assembly of a homogeneous catalyst in a fibrous network of multiwalled carbon nanotubes (MWNTs). Dimerization of an amide‐based chiral ligand with a suitable spacer allows for the efficient formation of a heterogeneous catalyst by self‐assembly on addition of Er(OiPr)3. The self‐assembly proceeds in the MWNT fibrous network and small

  基于均相催化剂在多壁碳纳米管（MWNTs）纤维网络中的自组装，已经开发了一种易于回收的不对称催化剂。酰胺基手性配体与合适的间隔基二聚可通过添加Er（O i Pr）3进行自组装，有效地形成非均相催化剂。自组装在MWNT纤维网络中进行，组装好的催化剂的小团簇被限制在MWNT中，产生易于处理的固相催化剂。所得的MWNT受限催化剂在催化不对称曼尼希型反应中表现出良好的催化性能，可以在重复批处理系统和连续流平台中进行。
• Asymmetric Catalysis via Dynamic Substrate/Ligand/Rare Earth Metal Conglomerate
  作者：Akihiro Nojiri、Naoya Kumagai、Masakatsu Shibasaki

  DOI：10.1021/ja800326d

  日期：2008.4.1

  A highly enantio- and diastereoselective catalytic asymmetric Mannich-type reaction of acyanoketones and N-Boc imines promoted by an amide ligand/Sc(OiPr)(3) catalyst is described. The similar reaction outcome is obtained with/without precomplexation of catalyst, suggesting that reaction i components in a non-ordered conglomerate mixture orchestrate to form an ordered transition state during the reaction. Spectroscopic data and Eyring plot are consistent with this assumption.