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Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation01:27

Cyclohexenones via Michael Addition and Aldol Condensation: The Robinson Annulation

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Robinson annulation is a base-catalyzed reaction for the synthesis of 2-cyclohexenone derivatives from 1,3-dicarbonyl donors (such as cyclic diketones, β-ketoesters, or β-diketones) and α,β-unsaturated carbonyl acceptors. Named after Sir Robert Robinson, who discovered it, this reaction yields a six-membered ring with three new C–C bonds (two σ bonds and one π bond).
2.3K
Ketones with Nonenolizable Aromatic Aldehydes: Claisen–Schmidt Condensation01:01

Ketones with Nonenolizable Aromatic Aldehydes: Claisen–Schmidt Condensation

3.8K
Benzaldehyde, like formaldehyde, lacks an α hydrogen and cannot enolize to form an enolate. Hence, the reaction of benzaldehyde with a ketone in the presence of an aqueous base forms a single crossed product. This reaction is referred to as Claisen–Schmidt condensation.
As the self-condensation of ketones is generally not favored in basic conditions, the self-condensed products do not form in the reaction between ketones and benzaldehyde. The general reaction of Claisen–Schmidt...
3.8K
Preparation of Alkynes: Dehydrohalogenation02:34

Preparation of Alkynes: Dehydrohalogenation

16.4K
Introduction
Alkynes can be prepared by dehydrohalogenation of vicinal or geminal dihalides in the presence of a strong base like sodium amide in liquid ammonia. The reaction proceeds with the loss of two equivalents of hydrogen halide (HX) via two successive E2 elimination reactions.
16.4K
Preparation of Alkynes: Alkylation Reaction02:27

Preparation of Alkynes: Alkylation Reaction

10.7K
Introduction
Alkylation of terminal alkynes with primary alkyl halides in the presence of a strong base like sodium amide is one of the common methods for the synthesis of longer carbon-chain alkynes. For example, treatment of 1-propyne with sodium amide followed by reaction with ethyl bromide yields 2-pentyne.
10.7K
Cycloaddition Reactions: Overview01:16

Cycloaddition Reactions: Overview

2.8K
Cycloadditions are one of the most valuable and effective synthesis routes to form cyclic compounds. These are concerted pericyclic reactions between two unsaturated compounds resulting in a cyclic product with two new σ bonds formed at the expense of π bonds. The [4 + 2] cycloaddition, known as the Diels–Alder reaction, is the most common. The other example is a [2 + 2] cycloaddition.
2.8K
Esters to β-Ketoesters: Claisen Condensation Mechanism01:08

Esters to β-Ketoesters: Claisen Condensation Mechanism

3.8K
Regular Claisen condensation involves the synthesis of β-ketoesters by combining identical ester molecules bearing two α hydrogens in the presence of an alkoxide base. The reaction commences with the deprotonation of the acidic α hydrogen by the base to form a resonance stabilized ester enolate. This nucleophilic ion then attacks the carbonyl center of another ester molecule to generate a tetrahedral alkoxide intermediate. Next, the expulsion of the alkoxide group from the...
3.8K

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Updated: Sep 11, 2025

Preparation of a Corannulene-functionalized Hexahelicene by CopperI-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units
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Preparation of a Corannulene-functionalized Hexahelicene by CopperI-catalyzed Alkyne-azide Cycloaddition of Nonplanar Polyaromatic Units

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通过碎片凝结方法合成单体甲基[4]arene.

Daniel Kortus1, Oliver Moravec1, Hynek Varga1

  • 1Department of Organic Chemistry, University of Chemistry and Technology Prague (UCTP), Technická 5, 166 28 Prague, Czech Republic.

Molecules (Basel, Switzerland)
|August 14, 2025
PubMed
概括

一种用于制备混合桥接 (CH2和S) [4]的新方法提供了高产. 可变温度的NMR研究揭示了这些宏观循环中的动态行为和键的洞察力.

关键词:
双醇 是一种双醇.卡利克萨雷内克萨雷内克萨雷尼形状的变化 形状的变化翻转机的机制是翻转机.碎片凝结凝结的时间宏观循环化的宏观循环化综合合成是一种合成.这是一种 thiacalixarene.温度变量的NMR是NMR.

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Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
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科学领域:

  • 超分子化学 超分子化学
  • 有机合成 有机合成
  • 宏观循环化学 宏观循环化学

背景情况:

  • 卡利克斯[4]是多功能宏循环平台.
  • 含硫的混合桥梁[4]沙具有独特的结构和动态特性.
  • 了解形状动态对于设计功能宏循环至关重要.

研究的目的:

  • 为了开发一个简单的和可扩展的合成2-monothiacalix[4]arene.
  • 为了研究合成的宏循环及其氧化衍生物的动态行为.
  • 阐明硫合并和氧化对宏环形状和结合的影响.

主要方法:

  • 通过线性双醇的凝结合成.
  • 可变温度的核磁共振 (NMR) 光谱学.
  • 动态过程的计算分析 (圆-圆倒置,翻转机械).

主要成果:

  • 通过使用两个替代途径,成功制备了高产量的2-monothiacalix[4]arene (7).
  • 对化合物7 (ΔG‡ = 63 kJ·mol−1) 和其硫衍生物14 (ΔG‡ = 60 kJ·mol−1) 的圆平衡和反转障碍的确定.
  • 在低温下 (ΔG‡ = 44 kJ·mol−1对于7而不是 ΔG‡ = 40 kJ·mol−1对于14) 的翻转键机制的障碍物的量化,表明硫中的键被削弱了.

结论:

  • 开发的合成策略有效地生产混合桥梁[4]arenes.
  • 硫的结合和氧化影响着在卡利克萨林框架内的结构动态和结.
  • 这些发现为含硫宏循环的结构性质关系提供了宝贵的见解.