基的基链的分子间循环化,用于构建基 - - 基
Chang Yin1,2, Hongyi Li1, Yanjing Liao1,2
1State Key Laboratory of Structural Chemistry, Fujian Science & Technology Innovation Laboratory for Optoelectronic Information of China, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Fujian, China.
Journal of the American Chemical Society
|February 3, 2026
概括
一种新的铜催化反应可以通过基醇链的分子间循环合成正氧基. 这种方法为复杂分子合成提供了高功能组耐受性和广泛的基质范围.
科学领域:
- 有机化学 有机化学
- 催化剂是一种催化剂.
- 合成方法论 合成方法论
背景情况:
- 甲基甲是药品和有机合成中有价值的构建模块.
- 通过基醇链的分子间循环有效合成正氧基是具有挑战性的.
研究的目的:
- 开发一种新的铜催化方法,用于合成正氧二甲.
- 探索这个新合成路线的范围和局限性.
主要方法:
- 基基底的铜催化分子间循环.
- 使用TEMPO (2,2,6,6-tetramethylpiperidin-1-yl) oxyl作为一种氧化剂.
- 通过替代的丁基对区域选择性的研究.
主要成果:
- 通过脱启动的分子间 [4 + 2] 循环.通过脱启动的分子间 [4 + 2] 循环实现的正氧甲基的区域选择性合成.
- 在各种基质中表现出高功能群耐受性.
- 取代的丁基产生了甲基亚基产物,表明了区域化学控制.
结论:
- 开发的铜催化反应提供了一个高效和多功能的路径,以ortho-diacylbenzenes.
- 该方法适用于从自然产品和生物活性化合物中提取的复杂.
- 反应机制涉及一种不寻常的电友性TEMPO催化 [4 + 2] 循环添加,绕过了典型的Diels-Alder要求.
相关概念视频
α-Alkylation of Ketones via Enolate Ions
3.9K
Ketones with α protons are deprotonated by strong bases like lithium diisopropylamide (LDA) to form enolate ions. The anion is stabilized by resonance, and its hybrid structure exhibits negative charges on the carbonyl oxygen and the α carbon. This ambident nucleophile can attack an electrophile via two possible sites: the carbonyl oxygen, known as O-attack, or the α carbon, known as C-attack. The nucleophilic attack via the carbanionic site is preferred. This is due to the...
3.9K
Intermolecular Forces in Solutions
39.6K
The formation of a solution is an example of a spontaneous process, a process that occurs under specified conditions without energy from some external source.
When the strengths of the intermolecular forces of attraction between solute and solvent species in a solution are no different than those present in the separated components, the solution is formed with no accompanying energy change. Such a solution is called an ideal solution. A mixture of ideal gases (or gases such as helium and argon,...
When the strengths of the intermolecular forces of attraction between solute and solvent species in a solution are no different than those present in the separated components, the solution is formed with no accompanying energy change. Such a solution is called an ideal solution. A mixture of ideal gases (or gases such as helium and argon,...
39.6K
Intermolecular Forces
71.4K
Atoms and molecules interact through bonds (or forces): intramolecular and intermolecular. The forces are electrostatic as they arise from interactions (attractive or repulsive) between charged species (permanent, partial, or temporary charges) and exist with varying strengths between ions, polar, nonpolar, and neutral molecules. The different types of intermolecular forces are ion–dipole, dipole–dipole, hydrogen bonds, and dispersion; among these, dipole–dipole, hydrogen...
71.4K
Factors Affecting α-Alkylation of Ketones: Choice of Base
3.6K
α-Alkylation of ketones is achieved in the presence of alkyl halides and a base. The reaction proceeds via the formation of an enolate ion followed by nucleophilic substitution. The choice of base employed is essential as it is the key factor in determining the reaction outcome.
The reaction involving bases like EtO− whose conjugate acid EtOH (pKa = 15.9) is stronger than the ketone (pKa = 19.2) results in an equilibrium mixture with higher ketone concentration. As a consequence,...
The reaction involving bases like EtO− whose conjugate acid EtOH (pKa = 15.9) is stronger than the ketone (pKa = 19.2) results in an equilibrium mixture with higher ketone concentration. As a consequence,...
3.6K
Intermolecular vs Intramolecular Forces
97.3K
Intermolecular forces (IMF) are electrostatic attractions arising from charge-charge interactions between molecules. The strength of the intermolecular force is influenced by the distance of separation between molecules. The forces significantly affect the interactions in solids and liquids, where the molecules are close together. In gases, IMFs become important only under high-pressure conditions (due to the proximity of gas molecules). Intermolecular forces dictate the physical properties of...
97.3K
Comparing Intermolecular Forces: Melting Point, Boiling Point, and Miscibility
51.5K
Intermolecular forces are attractive forces that exist between molecules. They dictate several bulk properties, such as melting points, boiling points, and solubilities (miscibilities) of substances. Molar mass, molecular shape, and polarity affect the strength of different intermolecular forces, which influence the magnitude of physical properties across a family of molecules.
Temporary attractive forces like dispersion are present in all molecules, whether they are polar or nonpolar. They...
Temporary attractive forces like dispersion are present in all molecules, whether they are polar or nonpolar. They...
51.5K


