非对称的反离子导向光反氧催化
Sayantani Das1, Chendan Zhu1, Derya Demirbas1
1Max-Planck-Institut für Kohlenforschung, D-45470 Mülheim an der Ruhr, Germany.
概括
研究人员开发了一种使用有机盐与特定对抗离子的不对称光催化方法. 这种方法可以实现烯的高度反选择性 [2+2] 交叉循环添加,克服以前的选择性挑战.
科学领域:
- 有机化学
- 催化剂
- 不对称的合成
背景情况:
- 氧催化提供了独特的反应途径,但与选择性,特别是反选择性作斗争.
- 在 photoredox 催化过程中的激素离子中间体中实现 enantioselectivity 是一个挑战.
- 现有的方法通常需要双激活模式来实现不对称的诱导.
研究的目的:
- 开发一种涉及基离子的对抗选择性光反氧催化剂的通用解决方案.
- 为了研究在光氧反应中控制选择性而使用的反素.
- 在 [2+2] 交叉循环添加烯中实现高反选择性.
主要方法:
- 开发含有封闭型二胺酸的新型有机盐.
- 这些盐在不对称的光电还原催化剂中的应用.
- styrenes 的 [2+2] 交叉循环添加反应的催化.
主要成果:
- 对基于基离子的不对称光电还原催化剂的潜在通用解决方案的演示.
- 实现了高度反选择性的 [2+2] 交叉循环添加的烯.
- 开发的有机盐有效控制了反选择性.
结论:
- 能有效地与光反氧催化剂配对以实现不对称的诱导.
- 新型的 imidodiphosphorimidate 对抗离子为对抗选择性基离子催化提供了强大的工具.
- 这项工作为控制光反反应的选择性开辟了新的途径.
相关概念视频
Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
3.4K
Catalytic hydrogenation of alkenes is a transition-metal catalyzed reduction of the double bond using molecular hydrogen to give alkanes. The mode of hydrogen addition follows syn stereochemistry.
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
3.4K
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
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
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
Woodward–Hoffmann Selection Rules and Microscopic Reversibility
3.2K
Electrocyclic reactions, cycloadditions, and sigmatropic rearrangements are concerted pericyclic reactions that proceed via a cyclic transition state. These reactions are stereospecific and regioselective. The stereochemistry of the products depends on the symmetry characteristics of the interacting orbitals and the reaction conditions. Accordingly, pericyclic reactions are classified as either symmetry-allowed or symmetry-forbidden. Woodward and Hoffmann presented the selection criteria for...
3.2K
Oxidation of Alkenes: Syn Dihydroxylation with Osmium Tetraoxide
10.6K
Alkenes are converted to 1,2-diols or glycols through a process called dihydroxylation. It involves the addition of two hydroxyl groups across the double bond with two different stereochemical approaches, namely anti and syn. Dihydroxylation using osmium tetroxide progresses with syn stereochemistry.
10.6K
![[DPEPhosbcpCu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)

