(R)-2-((S)-tert-butoxycarbonylamino)benzyl-2-cyanocyclopentanone | 1023754-71-3

• 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: (R)-2-((S)-tert-butoxycarbonylamino)benzyl-2-cyanocyclopentanone
• 英文别名: tert-butyl N-[(S)-[(1R)-1-cyano-2-oxocyclopentyl]-phenylmethyl]carbamate
• CAS: 1023754-71-3
• 化学式: C₁₈H₂₂N₂O₃
• 分子量: 314.384
• InChiKey: HTBPRBXDDBTGPK-MAUKXSAKSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3
• 重原子数：
  23
• 可旋转键数：
  5
• 环数：
  2.0
• sp3杂化的碳原子比例：
  0.5
• 拓扑面积：
  79.2
• 氢给体数：
  1
• 氢受体数：
  4

反应信息

• 作为产物：
  描述：

  benzaldehyde N-boc imine 、 2-氰基环戊酮 在 scandium isopropoxide 、 (S)-N-(2-hydroxyphenyl)-2-(2-hydroxybenzoylamino)-3-methylbutylamide 作用下， 以 四氢呋喃 、 乙酸乙酯 为溶剂， 生成 (R)-2-((S)-tert-butoxycarbonylamino)benzyl-2-cyanocyclopentanone 、 tert-butyl (S)-((S)-1-cyano-2-oxocyclopentyl)(phenyl)methylcarbamate
  参考文献：
  名称：

  Linking Structural Dynamics and Functional Diversity in Asymmetric Catalysis

  摘要：

  Proteins, the functional molecules in biological systems, are sophisticated chemical devices that have evolved over billions of years. Their function is intimately related to their three-dimensional structure and elegantly regulated by conformational changes through allosteric regulators and a number of reversible or unidirectional post-translational modifications. This functional diversification in response to external stimuli allows for an orderly and timely progression of intra- and extracellular events. In contrast, enantioselective catalysts generally exhibit limited conformational flexibility and thereby exert a single specific function. Exploiting the features of conformationally flexible asymmetric ligands and the variable coordination patterns of rare earth metals, we demonstrate dynamic structural and functional changes of a catalyst in asymmetric catalysis, leading to two distinct reaction outcomes in a single flask.

  DOI：

  10.1021/ja900084k

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）。
• Thiourea fused γ-amino alcohol organocatalysts for asymmetric Mannich reaction of β-keto active methylene compounds with imines
  作者：Miku Nomura、Zubeda Begum、Chigusa Seki、Yuko Okuyama、Eunsang Kwon、Koji Uwai、Michio Tokiwa、Suguru Tokiwa、Mitsuhiro Takeshita、Hiroto Nakano

  DOI：10.1039/d2ra08317e

  日期：——

  asymmetric Mannich reaction of β-keto active methylene compounds with imines to afford chiral Mannich products, β-amino keto compounds, with continuous chiral centers, that are versatile synthetic intermediates for deriving various biologically active compounds. In particular, the thiourea fused γ-amino alcohols showed satisfactory catalytic activity in this reaction and afforded chiral Mannich products

  在β-酮活性亚甲基化合物与亚胺的不对称曼尼希反应中检查了新型光学活性硫脲稠合γ-氨基醇的催化功能，以提供手性曼尼希产物，β-氨基酮化合物，具有连续手性中心，是通用的合成中间体用于衍生各种生物活性化合物。特别是，硫脲稠合的γ-氨基醇在此反应中表现出令人满意的催化活性，并以优异的化学产率（高达88%）和立体选择性（高达syn : anti /93 : 7 dr，高达99%）提供手性曼尼希产物。 ee）。
• 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.
• Solvent-Dependent Self-Discrimination of Bis(2-hydroxyphenyl)diamides
  作者：Akinobu Matsuzawa、Akihiro Nojiri、Naoya Kumagai、Masakatsu Shibasaki

  DOI：10.1002/chem.201000321

  日期：——

  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.