reactive intermediates
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2022 ◽  
Author(s):  
Z.-W. Hou ◽  
H.-C. Xu

Nitrogen-centered radicals are versatile reactive intermediates for organic synthesis. This chapter describes recent progress in the electrochemical generation and reactions of nitrogen-centered radicals. Under electrochemical conditions, various nitrogen-centered radicals are generated through electrolysis of readily available precursors such as N—H bonds or azides. These reactive intermediates undergo addition reactions to π-systems or hydrogen-atom abstraction to generate various nitrogen-containing compounds.


2022 ◽  
Author(s):  
Sofia Goia ◽  
Matthew A. P. Turner ◽  
Jack M. Woolley ◽  
Michael D. Horbury ◽  
Alexandra J. Borrill ◽  
...  

A spectroelectrochemical set-up using a boron doped diamond mesh electrode is presented; from ultrafast photodynamics to steady-state, the photochemistry and photophysics of redox active species and their reactive intermediates can be investigated.


2022 ◽  
Author(s):  
Brandon J Jolly ◽  
Nathalie H Co ◽  
Ashton R Davis ◽  
Paula L. Diaconescu ◽  
Chong Liu

Compartmentalization is an attractive approach to enhance catalytic activity by retaining reactive intermediates and mitigating deactivating pathways. Such a concept has been well explored in biochemical and more recently, organometallic...


2021 ◽  
Vol 119 (1) ◽  
pp. e2111938119
Author(s):  
Cheng Zhu ◽  
N. Fabian Kleimeier ◽  
Andrew M. Turner ◽  
Santosh K. Singh ◽  
Ryan C. Fortenberry ◽  
...  

Geminal diols—organic molecules carrying two hydroxyl groups at the same carbon atom—have been recognized as key reactive intermediates by the physical (organic) chemistry and atmospheric science communities as fundamental transients in the aerosol cycle and in the atmospheric ozonolysis reaction sequence. Anticipating short lifetimes and their tendency to fragment to water plus the aldehyde or ketone, free geminal diols represent one of the most elusive classes of organic reactive intermediates. Here, we afford an exceptional glance into the preparation of the previously elusive methanediol [CH2(OH)2] transient—the simplest geminal diol—via energetic processing of low-temperature methanol–oxygen ices. Methanediol was identified in the gas phase upon sublimation via isomer-selective photoionization reflectron time-of-flight mass spectrometry combined with isotopic substitution studies. Electronic structure calculations reveal that methanediol is formed via excited state dynamics through insertion of electronically excited atomic oxygen into a carbon–hydrogen bond of the methyl group of methanol followed by stabilization in the icy matrix. The first preparation and detection of methanediol demonstrates its gas-phase stability as supported by a significant barrier hindering unimolecular decomposition to formaldehyde and water. These findings advance our perception of the fundamental chemistry and chemical bonding of geminal diols and signify their role as an efficient sink of aldehydes and ketones in atmospheric environments eventually coupling the atmospheric chemistry of geminal diols and Criegee intermediates.


2021 ◽  
Author(s):  
Jichao Xiao ◽  
John Montgomery

A simple procedure is reported for the nickel-catalyzed defluorinative alkylation of unactivated aliphatic aldehydes. The process involves the catalytic reductive union of trifluoromethyl styrenes with aldehydes using a nickel complex of a 6,6’-disubstituted bipyridine ligand with zinc metal as the terminal reductant. The protocol is distinguished by its broad substrate scope, mild conditions, and simple catalytic setup. Reaction outcomes are consistent with the intermediacy of an alpha-silyloxy(alkyl)nickel intermediate generated by a low-valent nickel catalyst, silyl electrophile, and the aldehyde substrate. Mechanistic findings with cyclopropanecarboxaldehyde provide insights into nature of the reactive intermediates and illustrate fundamental reactivity differences that are governed by subtle changes in ligand and substrate structure.


2021 ◽  
pp. 679-714
Author(s):  
Moushumi Lahiri ◽  
Hasan Mukhtar ◽  
Rajesh Agarwal

2021 ◽  
Author(s):  
Diana Wang ◽  
Karina Targos ◽  
Zachary Wickens

Allylic amines are valuable synthetic targets en route to diverse biologically active amine products. Current allylic C–H amination strate-gies remain limited with respect to the viable N-substituents. Herein we disclose a new electrochemical process to prepare aliphatic allylic amines by coupling two abundant starting materials: secondary amines and unactivated alkenes. This oxidative transformation proceeds via electrochemical generation of an electrophilic adduct between thianthrene and the alkene substrates. Treatment of these adducts with aliphatic amine nucleophiles and base provides allylic amine products in high yield. This synthetic strategy is also amenable to functionali-zation of feedstock gaseous alkenes at 1 atmosphere. In the case of 1-butene, remarkable Z-selective crotylation is observed. This strategy, however, is not limited to the synthesis of simple building blocks; complex biologically active molecules are suitable as both alkene and amine coupling partners. Preliminary mechanistic studies implicate vinylthianthrenium salts as key reactive intermediates.


2021 ◽  
Vol 22 (21) ◽  
pp. 11751
Author(s):  
Shosuke Ito ◽  
Hitomi Tanaka ◽  
Makoto Ojika ◽  
Kazumasa Wakamatsu ◽  
Manickam Sugumaran

Neurogenerative diseases, such as Parkinson’s disease, are associated, not only with the selective loss of dopamine (DA), but also with the accumulation of reactive catechol-aldehyde, 3,4-dihydroxyphenylacetaldehyde (DOPAL), which is formed as the immediate oxidation product of cytoplasmic DA by monoamine oxidase. DOPAL is well known to exhibit toxic effects on neuronal cells. Both catecholic and aldehyde groups seem to be associated with the neurotoxicity of DOPAL. However, the exact cause of toxicity caused by this compound remains unknown. Since the reactivity of DOPAL could be attributed to its immediate oxidation product, DOPAL-quinone, we examined the potential reactions of this toxic metabolite. The oxidation of DOPAL by mushroom tyrosinase at pH 5.3 produced conventional DOPAL-quinone, but oxidation at pH 7.4 produced the tautomeric quinone-methide, which gave rise to 3,4-dihydroxyphenylglycolaldehyde and 3,4-dihydroxybenzaldehyde as products through a series of reactions. When the oxidation reaction was performed in the presence of ascorbic acid, two additional products were detected, which were tentatively identified as the cyclized products, 5,6-dihydroxybenzofuran and 3,5,6-trihydroxybenzofuran. Physiological concentrations of Cu(II) ions could also cause the oxidation of DOPAL to DOPAL-quinone. DOPAL-quinone exhibited reactivity towards the cysteine residues of serum albumin. DOPAL-oligomer, the oxidation product of DOPAL, exhibited pro-oxidant activity oxidizing GSH to GSSG and producing hydrogen peroxide. These results indicate that DOPAL-quinone generates several toxic compounds that could augment the neurotoxicity of DOPAL.


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