Search results for "HILIC"

Quasi-RRHO approximation and DFT study for understanding the mechanism and kinetics of nitration reaction of benzonitrile with nitronium ion

2021

Abstract The nitration reaction of benzonitrile with nitronium cation, NO2+, has been studied within the Molecular Electron Density Theory at the MN15-L/aug-cc-pVTZ level of theory. For this electrophilic aromatic substitution (EAS) reaction, three regioisomeric reaction paths have been studied. Quasi-RRHO approximation was applied to consider the vibrational contribution to entropy and correct the Gibbs free energy profile of the reaction in the solvent phase. Benzonitrile is less nucleophilically activated than benzene due to the presence of the electron-withdrawing CN group the meta position is the more favorable reaction path of this EAS reaction. The analysis of ELF and AIM demonstrate…

2020

The course of organic chemical reactions is efficiently modelled through the concepts of “electrophiles” and “nucleophiles” (meaning electron-seeking and nucleus-seeking reactive species). On the one hand, an advanced approach of the correlation of the nucleophilicity parameters N and electrophilicity E has been delivered from the linear free energy relationship log k (20 °C) = s(N + E). On the other hand, the general influence of the solvent mixtures, which are very often employed in preparative synthetic chemistry, has been poorly explored theoretically and experimentally, to date. Herein, we combined experimental and theoretical studies of the solvent influence on pyrrolidine nucleophili…

Arene C−H Activation at Aluminium(I): meta Selectivity Driven by the Electronics of S N Ar Chemistry

2020

The reactivity of the electron-rich anionic Al(I) ('aluminyl') compound K 2 [(NON)Al] 2 (NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di- tert -butyl-9,9-dimethylxanthene) towards mono- and disubstituted arenes is reported. C-H activation chemistry with n -butylbenzene gives exclusively the product of activation at the arene meta position. Mechanistically, this transformation proceeds in a single step via a concerted Meisenheimer-type transition state. Selectivity is therefore based on similar electronic factors to classical S N Ar chemistry, which implies the destabilization of transition states featuring electron-donating groups in either the ortho or the para positions. In the cases of tolu…

Regio-, Diastereo-, and Enantioselective Organocatalytic Addition of 4-Substituted Pyrazolones to Isatin-Derived Nitroalkenes

2019

"This is the peer reviewed version of the following article: [FULL CITE], which has been published in final form at [Link to final article using the DOI]. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving."

Preparative-Scale Synthesis of Vedejs Chiral DMAP Catalysts

2018

A scalable synthesis of chiral Vedejs-type DMAP catalysts is reported. The key step of the synthesis is amination of the enantiomerically pure 4-chloropyridine derivative using well-defined ZnCl2(amine)2 complexes. A series of Zn(II)–amine complexes have been synthesized to explore the scope of the ZnCl2-mediated amination of 4-halopyridines. Mechanistic studies support a Zn(II)-facilitated nucleophilic aromatic substitution as a plausible mechanism for the chlorine-to-amine exchange.

Total Synthesis of (-)-Oxycodone via Anodic Aryl-Aryl Coupling.

2019

A fully regio- and diastereoselective electrochemical 4a–2′-coupling of a 3′,4′,5′-trioxygenated laudanosine derivative enables the synthesis of the corresponding morphinandienone. This key intermediate is further transformed into (−)-oxycodone through conjugate nucleophilic substitution for E-ring closure and [4 + 2] cycloaddition with photogenerated singlet oxygen to accomplish diastereoselective hydroxylation at C-14. The anodic transformation provides high yields and can be performed under constant current conditions both in a simple undivided cell or in continuous flow.

The aminophosphonate glyphosine enhances phycobiliprotein yields from selected cyanobacterial cultures

2017

Among added-value products obtained from cyanobacterial cultures are phycobiliproteins, photosynthetic pigments that have found an increasing number of applications as natural dyes for food, cosmetics, pharmaceuticals, and antioxidants. To obtain sustainable production, we aimed at maximizing phycobilin yield through the increase of either the final biomass or the specific content of these pigments by varying culture parameters, such as chemical composition and pH of the medium or quality and intensity of the light. Here, we report that the addition to the culture medium of millimolar or submillimolar concentrations of the aminophosphonate glyphosine [(N,N-bis(phosphonomethyl)glycine], form…

Unveiling the diet of the thermophilic starfish Ophidiaster ophidianus (Echinodermata: Asteroidea) combining visual observation and stable isotopes a…

2020

The starfish Ophidiaster ophidianus is an Atlanto-Mediterranean species protected under the EU’s Habitat Directive. Despite the wide distribution and the current range of expansion of this thermophilic species in the northern Mediterranean Sea, nothing is known about its diet. Using field observations and δ13C and δ15N Stable Isotopes Analysis (SIA), the feeding habits of O. ophidianus were explored in two Mediterranean rocky reef areas located in the southern Tyrrhenian (Ustica Island, Italy) and the eastern Adriatic Sea (Molunat, Croatia). According to field observations, O. ophidianus preys mainly on crustose coralline algae (CCA) and the keratose sponge Ircinia variabilis in both areas.…

Effect of Seasonal Storage on Single-Stem Bark Extractives of Norway Spruce (Picea abies)

2021

Increasing the net value of forestry side-streams has both ecological as well as economic benefits for emerging biorefining industries. Spruce bark represents one of the nature’s abundant sources of valuable extractives. In this study, the impact of storage on the quality and quantity of Norway spruce (Picea abies) extractives was examined as a function of storage time, environmental conditions and season (i.e., winter or summer). The bark from stored spruce saw logs was extracted with an accelerated solvent extractor (ASE) at 120 °C with hexane and water. The produced extracts were analysed qualitatively and quantitatively by gas chromatography with a flame ionisation detector (GC-FID) and…

Risk of Invasive Lupinus polyphyllus Seed Survival in Biomass Treatment Processes

2021

Invasive plant species threaten native species and habitats causing ecologic, economic and social burden. When creating climate friendly solutions by utilizing plant biomasses in biogas and fertilizer production, safety should be ensured concerning the use of residues. This study concentrates on the treatment of biomasses containing invasive plant material by tunnel and windrow composting, and by farm-scale and laboratory-scale anaerobic digestion (AD) in mesophilic conditions. Germination of the nationally settled and harmful invasive species Lupinus polyphyllus Lindl. was investigated after these processes. In addition, the role of the conditions found in the processes that destroyed seed…