不被激活的氨酸的分子间光学催化循环化
David M Fischer1, Henry Lindner1, Willi M Amberg1
1Laboratory of Organic Chemistry, Department of Chemistry and Applied Biosciences, ETH Zürich, 8093 Zurich, Switzerland.
Journal of the American Chemical Society
|January 6, 2023
概括
这项研究引入了一种有机光催化方法,用于从烯酸和烯酸中制造高度替代的环烯酸. 这种高效的反应在温和条件下与多种功能组合作, 提供了一种新的合成途径.
科学领域:
- 有机化学
- 光催化
- 合成方法
背景情况:
- 环烯是药品和材料中的有价值的结构图案.
- 高度替代环的有效和选择性合成仍然是一个挑战.
- 有机光催化提供了一种可持续和温和的方法来处理复杂的有机变化.
研究的目的:
- 使用器官光催化剂开发一种新的分子间循环化反应.
- 从易于获得的原料中合成高度替代的环烯.
- 探索开发的方法的范围和局限性.
主要方法:
- 用α--β-基和α-马隆酸盐进行分子间环.
- 使用西诺素衍生物作为机体光催化剂.
- 在温和反应条件下使用可见光照射.
主要成果:
- 这种反应成功地产生了具有广泛功能群耐受性的高度替代性环烯.
- 基质包括单基,二基和三基替代的烯和各种功能组,如酸,醇和.
- 在有氧和水性条件下,转化在低催化剂负载 (0.5mol%) 的情况下进行得很有效.
结论:
- 已经建立了一种新高效的有机光催化方法.
- 反应提供了多样化和高度替代的环烯.
- 机理学研究支持拟议的催化循环,强调了这种方法对复杂分子合成的潜力.
相关概念视频
Cycloaddition Reactions: MO Requirements for Photochemical Activation
2.2K
Some cycloaddition reactions are activated by heat, while others are initiated by light. For example, a [2 + 2] cycloaddition between two ethylene molecules occurs only in the presence of light. It is photochemically allowed but thermally forbidden.
2.2K
Cycloaddition Reactions: MO Requirements for Thermal Activation
3.6K
Thermal cycloadditions are reactions where the source of activation energy needed to initiate the reaction is provided in the form of heat. A typical example of a thermally-allowed cycloaddition is the Diels–Alder reaction, which is a [4 + 2] cycloaddition. In contrast, a [2 + 2] cycloaddition is thermally forbidden.
3.6K
Photochemical Electrocyclic Reactions: Stereochemistry
1.9K
The absorption of UV–visible light by conjugated systems causes the promotion of an electron from the ground state to the excited state. Consequently, photochemical electrocyclic reactions proceed via the excited-state HOMO rather than the ground-state HOMO. Since the ground- and excited-state HOMOs have different symmetries, the stereochemical outcome of electrocyclic reactions depends on the mode of activation; i.e., thermal or photochemical.
Selection Rules: Photochemical Activation
Selection Rules: Photochemical Activation
1.9K
Thermal and Photochemical Electrocyclic Reactions: Overview
2.4K
Electrocyclic reactions are reversible reactions. They involve an intramolecular cyclization or ring-opening of a conjugated polyene. Shown below are two examples of electrocyclic reactions. In the first reaction, the formation of the cyclic product is favored. In contrast, in the second reaction, ring-opening is favored due to the high ring strain associated with cyclobutene formation.
2.4K
ortho–para-Directing Activators: –CH3, –OH, –⁠NH2, –OCH3
6.2K
All ortho–para directors, excluding halogens, are activating groups. These groups donate electrons to the ring, making the ring carbons electron-rich. Consequently, the reactivity of the aromatic ring towards electrophilic substitution increases. For instance, the nitration of anisole is about 10,000 times faster than the nitration of benzene. The electron-donating effect of the methoxy group in anisole activates the ortho and para positions on the ring and stabilizes the corresponding...
6.2K
Thermal Electrocyclic Reactions: Stereochemistry
2.1K
The stereochemistry of electrocyclic reactions is strongly influenced by the orbital symmetry of the polyene HOMO. Under thermal conditions, the reaction proceeds via the ground-state HOMO.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
Selection Rules: Thermal Activation
Conjugated systems containing an even number of π-electron pairs undergo a conrotatory ring closure. For example, thermal electrocyclization of (2E,4E)-2,4-hexadiene, a conjugated diene containing two π-electron pairs, gives trans-3,4-dimethylcyclobutene.
2.1K


