N-(tert-butyl)-2-oxocyclopentanecarboxamide | 1048671-72-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: N-(tert-butyl)-2-oxocyclopentanecarboxamide
• 英文别名: N-(t-butyl)-2-oxocyclopentane-1-carboxamide；N-tert-butyl-2-oxocyclopentane-1-carboxamide
• CAS: 1048671-72-2
• 化学式: C₁₀H₁₇NO₂
• 分子量: 183.25
• InChiKey: APYCLFZIHNNHEI-UHFFFAOYSA-N

物化性质

• 沸点：
  357.0±31.0 °C(Predicted)
• 密度：
  1.048±0.06 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  1.5
• 重原子数：
  13
• 可旋转键数：
  2
• 环数：
  1.0
• sp3杂化的碳原子比例：
  0.8
• 拓扑面积：
  46.2
• 氢给体数：
  1
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-(tert-butyl)-2-oxocyclopentanecarboxamide 在 N-(苯磺酰基)-N-甲基苯磺酰胺 、 C₁₀₄H₉₈O₂P₄Pd₂⁽²⁺⁾*2CF₃O₃S^(1-) 作用下， 以 丙酮 为溶剂， 反应 12.0h， 以72%的产率得到(R)-1-fluoro-2-oxo-N-(tert-butyl)cyclopentanecarboxamide
  参考文献：
  名称：

  Unique features of chiral palladium enolates derived from β-ketoamide: structure and catalytic asymmetric Michael and fluorination reactions

  摘要：

  We have previously reported enantioselective reactions of 1,3 -diketones and beta-ketoesters with various electrophiles catalyzed by chiral Pd complex, in which chiral Pd enolates play a key role. Here, we present a detailed examination of Pd-catalyzed enantioselective Michael addition and fluorination reactions of beta-ketoamides. beta-Ketoamide showed higher reactivity than 1,3-diketone and beta-ketoester, though its alpha-proton is likely to be least acidic. Pd enolate formation of beta-ketoamide was much faster than that of beta-ketoester. The crystal structures of (R)-BINAP-Pd-diketone and ketoamide complexes were found to be quite distinct. Pd-diketone complex has bidentate square-planar geometry as have been predicted before, whereas Pd-ketoamide complex was greatly distorted, probably due to steric constraints of the amide bond. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.07.002
• 作为产物：
  描述：

  1-(1-吡咯烷)环戊烯 在 水 、 溶剂黄146 作用下， 以 四氢呋喃 、 甲苯 为溶剂， 反应 22.0h， 生成 N-(tert-butyl)-2-oxocyclopentanecarboxamide
  参考文献：
  名称：

  Unique features of chiral palladium enolates derived from β-ketoamide: structure and catalytic asymmetric Michael and fluorination reactions

  摘要：

  We have previously reported enantioselective reactions of 1,3 -diketones and beta-ketoesters with various electrophiles catalyzed by chiral Pd complex, in which chiral Pd enolates play a key role. Here, we present a detailed examination of Pd-catalyzed enantioselective Michael addition and fluorination reactions of beta-ketoamides. beta-Ketoamide showed higher reactivity than 1,3-diketone and beta-ketoester, though its alpha-proton is likely to be least acidic. Pd enolate formation of beta-ketoamide was much faster than that of beta-ketoester. The crystal structures of (R)-BINAP-Pd-diketone and ketoamide complexes were found to be quite distinct. Pd-diketone complex has bidentate square-planar geometry as have been predicted before, whereas Pd-ketoamide complex was greatly distorted, probably due to steric constraints of the amide bond. (C) 2015 Elsevier Ltd. All rights reserved.

  DOI：

  10.1016/j.tet.2015.07.002

文献信息

• Identification of new biologically active synthetic molecules: comparative experimental and theoretical studies on the structure-antioxidant activity relationship of cyclic 1,3-ketoamides
  作者：Riad Mustapha Kerbadou、Ratiba Hadjadj Aoul、Aouicha Benmaati、Assya Taleb、Salih Hacini、Hadjira Habib Zahmani

  DOI：10.1007/s00894-021-04705-4

  日期：2021.4

  Antioxidant agent is a chemical that prevents the oxidation of other chemical substances. Its use is the most effective means of protecting the organism by neutralizing the harmful effects of free radicals caused by oxidative stress. In the present work, a series of β-ketoamides containing a variety of monosubstituted amide groups were synthesized and tested as antioxidant agents. In order to establish

  抗氧化剂是一种防止其他化学物质氧化的化学物质。它的使用是通过中和氧化应激引起的自由基的有害影响来保护生物体的最有效手段。在目前的工作中，合成了一系列含有多种单取代酰胺基团的 β-酮酰胺，并作为抗氧化剂进行了测试。为了建立可能的结构-抗氧化活性关系，我们正在对这些分子进行系统的理论研究，目的是阐明活性位点。特别是，我们讨论了选择自由基/抗氧化系统所产生的选择性。这些分子的理论研究是在 B3LYP/6-311G (d,p) 理论水平上使用密度泛函理论 (DFT) 计算进行的。为了阐明 β-酮酰胺的抗氧化性能，O-H 键解离焓 (BDE)、电离势 (IP)、电子亲和 (EA)、质子亲和 (PA) 和电子转移焓 (ETE) 是在气相和乙醇中进行。获得的结果表明，HAT 机制在气相中在热力学上更有利，而 SPLET 在极性溶剂中更受欢迎。
• Eco-Friendly Access to β -Ketoamides: one-step Catalyst - and solvent-free Amidation of β -Ketoesters under Microwave Irradiation
  作者：Khadidja Dechira、Assya Taleb、Aouicha Benmaati、Salih Hacini、Hadjira Habib Zahmani

  DOI：10.13005/ojc/340117

  日期：2018.2.28

  A highly efficient and facile catalyst- and solvent-free one step amidation of β-ketoesters, without using any additional reagents, is described. Therefore, β-ketoamides are obtained in good to excellent yields by condensation of β-ketoesters with various primary or secondary amines. This eco-friendly protocol has been developed under microwave irradiation.

  描述了一种高效且简便的催化剂和溶剂无关的一步氨化反应，可以在不使用任何额外试剂的情况下进行。因此，通过β-酮酯与各种初级或次级胺的缩合反应，获得了良好至优异产率的β-酮酰胺。这种环保的程序是在微波辐射下开发的。
• User-friendly stereoselective one-pot access to 1,4-diazepane derivatives by a cyclodehydrative three-component reaction with 1,3-dicarbonyls
  作者：Enrique Sotoca、Christophe Allais、Thierry Constantieux、Jean Rodriguez

  DOI：10.1039/b821343g

  日期：——

  A multicomponent reaction of 1,3-dicarbonyls with 1,2-diamines and aromatic aldehydes is described for the direct stereoselective synthesis of 1,4-diazepane derivatives. Various reaction conditions were tested, including an efficient, user-friendly solvent- and catalyst-free procedure.

  本文介绍了 1,3-二羰基与 1,2-二胺和芳香醛的多组分反应，用于直接立体选择性合成 1,4-二氮杂环庚烷衍生物。对各种反应条件进行了测试，包括一种高效、用户友好的无溶剂和无催化剂程序。
• Solvent- and Catalyst-Free Three-Component Reaction with β-Ketoamides for the Stereoselective One-Pot Access to 1,4-Diazepines
  作者：Thierry Constantieux、Jean Rodriguez、Enrique Sotoca

  DOI：10.1055/s-2008-1072787

  日期：2008.5

  The stereoselective one-pot synthesis of polysubstituted 1,4-diazepine derivatives has been achieved via a new solvent- and catalyst-free multicomponent domino reaction from β-ketoamides. This green and experimentally simple sequence is conducted from easily accessible achiral starting materials, does not require any harmful reagents, and results in a high increase in molecular complexity and diversity. Moreover, water is the only byproduct liberated during the reaction.

  通过一种新的无溶剂和催化剂的多组分多米诺反应，从δ²-酮酰胺出发，实现了多取代的 1,4-二氮杂卓衍生物的立体选择性一锅合成。这一绿色且实验简单的序列是从容易获得的非手性起始材料开始的，不需要任何有害试剂，并能增加分子的复杂性和多样性。此外，水是反应过程中释放出的唯一副产品。
• Regioselective and asymmetric allylic alkylation of vinyl epoxides for the construction of allylic alcohols via synergistic catalysis
  作者：Min Chen、Longqing Yang、Yuzhen Li、Yinhe Qu、Guihua Pan、Xiaoming Feng、Xiaohua Liu

  DOI：10.1007/s11426-023-1794-2

  日期：2024.2

  efficient asymmetric allylic alkylation of cyclic and acyclic carbon nucleophiles with vinyl epoxides has been developed, which exhibits good functional group compatibility, high atomic and step economy. This protocol utilizes a strategy of synergistic catalysis with a chiral N,N′-dioxide/NiII complex and an achiral Pd0 catalyst, generating a series of multi-substituted allylic alcohols with a quaternary

  开发了环状和无环碳亲核试剂与乙烯基环氧化物的高效不对称烯丙基烷基化反应，具有良好的官能团相容性、高原子和步骤经济性。该方案采用手性N , N′-二氧化物/Ni II配合物和非手性Pd 0催化剂的协同催化策略，以高产率和优异的区域性生成一系列具有季碳立构中心的多取代烯丙醇。Z / E-和温和条件下的对映选择性。产品的进一步转化证明了该方案在烯丙醇衍生物和天然产物类似物合成中的潜在用途。实验研究表明，N , N′-二氧化物/金属配合物在控制Z / E-和对映选择性方面发挥着重要作用。密度泛函理论（DFT）计算进一步表明，两种底物的芳环与配体中的酰胺部分之​​间的多个C–H;·;·;·π相互作用稳定了主要的过渡态。