通过坚固的金属有机框架促进的含气体的光化学基化
Jiachen He1, Joharimanitra Randrianandraina2, Husain Adamji3
1Department of Chemistry and Chemical Biology, Cornell University, Ithaca, New York 14850, United States.
Journal of the American Chemical Society
|December 30, 2025
概括
这项研究引入了一种使用金属有机框架 (Al-fum) 储存化气体的新方法,用于可持续的基化反应. 这种方法提高了原子的经济性,并使复杂的化物的有效合成成为可能.
科学领域:
- 有机化学
- 材料科学
- 可持续的化学
背景情况:
- 光化学对于可持续的合成至关重要,但晚期基化因传统试剂的原子经济性较差而受到限制.
- 在制药和农业化学品中具有关键作用,需要高效的合成方法.
研究的目的:
- 使用廉价的气体构建块开发光诱导基化的可持续平台.
- 通过使用气体Al-fum试剂来克服传统基化剂的局限性.
主要方法:
- 在金属有机框架Al-fum中储存简单的化气体.
- 开发了11种光诱导的基化反应,包括SH2,金属氧交联和 [2+2]循环添加.
- 使用气体剂量程序进行试剂制备和反应优化.
主要成果:
- 在Al-fum中储存化气体,产生稳定,可重复使用的试剂.
- 成功地将气体Al-fum系统应用于11种不同的光诱导基化反应.
- 通过反应优化和机理学研究证明了兼容性.
结论:
- 气体Al-fum系统为光化学中使用廉价气体构建块提供了一个一般平台.
- 这种方法为下一代化物的可持续合成铺平了道路.
- 该方法在基化中提供了更好的原子经济性和广泛的适用性.
相关概念视频
Electrophilic Aromatic Substitution: Fluorination and Iodination of Benzene
7.3K
Bromination and chlorination of aromatic rings by electrophilic aromatic substitution reactions are easily achieved, but fluorination and iodination are difficult to achieve. Fluorine is so reactive that its reaction with benzene is difficult to control, resulting in poor yields of monofluoroaromatic products. To address this, Selectfluor reagent is used as a fluorine source in which a fluorine atom is bonded to a positively charged nitrogen.
7.3K
Halogens
23.2K
Group 17 elements, known as halogens, are nonmetals. At room temperature, fluorine and chlorine are gases, bromine is a liquid, and iodine a solid. Astatine is a highly unstable radioactive element, so currently, most of its properties are unknown due to its short half-life. Tennessine is a synthetic element also predicted to be in this group.
23.2K
Hydroboration-Oxidation of Alkenes
10.9K
In addition to the oxymercuration–demercuration method, which converts the alkenes to alcohols with Markovnikov orientation, a complementary hydroboration-oxidation method yields the anti-Markovnikov product. The hydroboration reaction, discovered in 1959 by H.C. Brown, involves the addition of a B–H bond of borane to an alkene giving an organoborane intermediate. The oxidation of this intermediate with basic hydrogen peroxide forms an alcohol.
10.9K
Radical Anti-Markovnikov Addition to Alkenes: Mechanism
4.6K
The reaction of hydrogen bromide with alkenes in the presence of hydroperoxides or peroxides proceeds via anti-Markovnikov addition. The radical chain reaction comprises initiation, propagation, and termination steps.
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy...
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy...
4.6K
ortho–para-Directing Deactivators: Halogens
6.5K
Halogens are ortho–para directors. They are more electronegative than carbon. Therefore, as ring substituents, they can withdraw electrons through the inductive effect and deactivate the aromatic ring towards electrophilic substitution. Halogens also have an electron-donating resonance effect on the ring, which influences the orientation of the incoming electrophile. If an electrophile attacks at the ortho or the para position, the halogen donates electrons and stabilizes the intermediate...
6.5K
Alkyl Halides
19.4K
Structural Properties
Alkyl halides are halogen-substituted alkanes wherein one or more hydrogen atoms of an alkane is replaced by a halogen atom such as fluorine, chlorine, bromine, or iodine. The carbon atom in an alkyl halide is bonded to the halogen atom, which is sp3-hybridized and exhibits a tetrahedral shape.
Unlike alkyl halides, compounds in which a halogen atom is bonded to an sp2 -hybridized carbon atom of a carbon-carbon double bond (C=C) are called vinyl halides. Whereas aryl...
Alkyl halides are halogen-substituted alkanes wherein one or more hydrogen atoms of an alkane is replaced by a halogen atom such as fluorine, chlorine, bromine, or iodine. The carbon atom in an alkyl halide is bonded to the halogen atom, which is sp3-hybridized and exhibits a tetrahedral shape.
Unlike alkyl halides, compounds in which a halogen atom is bonded to an sp2 -hybridized carbon atom of a carbon-carbon double bond (C=C) are called vinyl halides. Whereas aryl...
19.4K


